JP6086387B2 - Method for producing carbon nanotube - Google Patents

Description

  The present invention relates to a method for producing a carbon nanotube (CNT) by using, as a template, a cyclic compound in which a plurality of aromatic rings are connected to hold a π-electron conjugated system.

  Conventionally, as a nanostructure containing a carbon atom, a carbon nanotube having a structure in which a two-dimensional graphene sheet is wound in a cylindrical shape is known.

  Since carbon nanotubes have properties such as high conductivity, high mechanical strength, excellent elasticity, heat resistance, and lightness, they can be used in various fields such as chemistry, electronics, and life science. Application is expected.

  Known methods for producing carbon nanotubes include, for example, an arc discharge method, a laser fanes method, a chemical vapor deposition method (CVD method), and the like. However, in these production methods, it is difficult to control the diameter and length of the tube, and there is a problem that it can be obtained only with a mixture of carbon nanotubes having various diameters and lengths. Since carbon nanotubes are desired to have uniform physical properties when used in the above applications, a method for selectively producing carbon nanotubes having a desired chemical structure is strongly demanded.

  In recent years, research on cycloparaphenylene compounds, which are the smallest structural units of carbon nanotubes, has been reported.

  For example, Non-Patent Document 1 discloses a method for producing a mixture of cycloparaphenylene compounds having a ring structure in which 9, 12 or 18 benzene rings are linked using 1,4-diiodobenzene and benzoquinone as raw materials. Is described.

  Non-Patent Documents 2 and 3 disclose a method for producing a cycloparaphenylene compound having a ring structure in which 12 benzene rings are regularly connected using 1,4-cyclohexanedione and 1,4-diiodobenzene. Is described.

  Non-Patent Document 4 describes a method for producing a cycloparaphenylene compound having a cyclic structure in which eight benzene rings are regularly connected by reductive elimination of a square biphenylene platinum complex with bromine.

  The cycloparaphenylene compound disclosed in the above non-patent document has a ring-shaped chemical structure in which a plurality of phenylene groups are linked by a single bond, and is the smallest structural unit of an armchair-type single-walled carbon nanotube (CNT). Has interesting physical properties.

Jasti, R. et al., J. Am. Chem. Soc., 2008, 130 (52), 17646 Itami, K. et al., Angew. Chem. Int. Ed., 2009, 48, 6112 Itami, K. et al., Angew. Chem. Int. Ed., 2010, 49, 10202 Yamago, S. et al., Angew. Chem. Int. Ed., 2009, 49, 757

  An object of the present invention is to provide a method for selectively producing carbon nanotubes having a desired diameter (hereinafter referred to as “CNT”).

  As a result of intensive studies to solve the above-mentioned problems, the present inventors used a cyclic compound in which a plurality of aromatic rings are connected and held a π-electron conjugated system as a template. It has been found that single-walled carbon nanotubes (SWCNTs) in which the diameter of the template ring is maintained can be produced by heat treatment with a carbon source.

  A typical template includes a cyclic compound formed by connecting divalent aromatic hydrocarbon groups. This is expressed as “carbon nanoring”. Specific examples of the carbon nanoring include “cycloparaphenylene compound” (see Non-Patent Documents 1 to 4), which is the shortest skeleton of an armchair single-walled carbon nanotube, and at least one phenylene group of the cycloparaphenylene compound. And “modified cycloparaphenylene compounds” and the like substituted with a divalent condensed polycyclic aromatic hydrocarbon group (for example, a 2,6-naphthylene group, etc.).

  According to the method for producing CNTs of the present invention, a graphene sheet is grown in the central axis direction of the cyclic compound by using the template (cyclic compound) and causing a carbon source to act on the template. Carbon nanotubes (CNT) having substantially the same size can be selectively produced. Therefore, the method of the present invention is a very innovative manufacturing method capable of selectively manufacturing CNTs having a substantially constant diameter. For example, FIG. 1 shows a schematic diagram in which an armchair single-walled carbon nanotube is formed by reacting a carbon source with a cycloparaphenylene compound ([n] CPP) in which n paraphenylenes are linked.

  As a result of further research based on this finding, the present invention has been completed.

  That is, the present invention provides the following carbon nanotube (CNT) production method and carbon nanotube (CNT).

  Item 1. A method for producing a carbon nanotube, comprising reacting a carbon source with a cyclic compound formed by connecting a plurality of aromatic rings.

  Item 2. Item 2. The production method according to Item 1, wherein the reaction is performed by supplying a gaseous carbon source and heating under reduced pressure.

  Item 3. Item 3. The production method according to Item 1 or 2, wherein the cyclic compound formed by connecting a plurality of aromatic rings is a cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups.

  Item 4. The cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups is a cycloparaphenylene compound, or at least one phenylene group of the cycloparaphenylene compound is a divalent condensed polycycle. Item 4. The production method according to Item 3, which is a modified cycloparaphenylene compound substituted with an aromatic hydrocarbon group.

  Item 5. The cyclic compound (carbon nanoring) formed by connecting the plurality of divalent aromatic hydrocarbon groups is represented by the general formula (1):

(In the formula, a represents an integer of 6 or more.)
Or at least one phenylene group of the cycloparaphenylene compound represented by the general formula (1) is represented by the general formula (2):

(In the formula, b represents an integer of 1 or more.)
Item 5. The production method according to Item 4, which is a modified cycloparaphenylene compound substituted with a group represented by the formula:

  Item 6. Item 6. The production method according to Item 5, wherein the cycloparaphenylene compound is a compound in which a in the general formula (1) is an integer of 6 to 100.

  Item 7. Item 7. The production method according to Item 5 or 6, wherein the cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups is a cycloparaphenylene compound represented by the general formula (1). .

  Item 8. The cyclic compound (carbon nanoring) formed by connecting the plurality of divalent aromatic hydrocarbon groups is represented by the general formula (3):

Wherein R ² is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; R ⁴ is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon Group is the same or different, and each is an integer of 0 or more; n is the same or different and each represents an integer of 1 or more.)
A cyclic compound represented by the general formula (4):

(In the formula, d represents an integer of 1 or more.)
Or a cyclic compound represented by the general formula (13):

(Wherein R ⁷ is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; l is 10, 11 or 13)
Item 4. The production method according to Item 3, which is a cyclic compound represented by:

  Item 9. Item 9. The production method according to any one of Items 1 to 8, wherein the carbon source is at least one selected from the group consisting of a hydrocarbon compound, an alcohol compound, an ether compound, and an ester compound.

Item 10. Item 10. The production method according to any one of Items 1 to 9, wherein the reaction is performed by heat treatment at 400 to 1200 ° C. under a pressure of 10 ⁻⁴ to 10 ⁵ Pa while supplying a gaseous carbon source.

  Item 11. A carbon nanotube obtained by reacting a carbon source with a cyclic compound formed by connecting a plurality of aromatic rings.

  Item 12. Item 12. The carbon nanotube according to Item 11, wherein the reaction is conducted by supplying a gaseous carbon source and heating under reduced pressure.

  Item 13. Item 13. The carbon nanotube according to Item 11 or 12, which is a single-walled carbon nanotube.

  According to the production method of the present invention, a single-walled carbon nanotube in which the diameter of the ring of the template is maintained by using a cyclic compound in which a plurality of aromatic rings are connected and a π-electron conjugated system is maintained as a template. SWCNTs) can be manufactured.

  As the template, for example, a cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups such as a cycloparaphenylene compound and a modified cycloparaphenylene compound can be used. Various templates can be selected and can be easily manufactured based on a known method and a method described in the present specification.

  By using the production method of the present invention, various CNTs such as an armchair type and a chiral type can be produced from the structure of the template. For example, if a cycloparaphenylene compound is used as a template, an armchair CNT having a certain diameter can be selectively produced. Further, if a modified cycloparaphenylene compound is used as a template, chiral CNTs having a certain diameter can be selectively produced.

  In the production method of the present invention, it is not necessary to use a catalyst that is indispensable in the conventional CNT production method, so that the separation work of the CNT obtained after the reaction and the catalyst is not required. In the conventional method, there are a large number of impurities due to the catalyst or the like used, but in the method of the present invention, highly pure CNT can be produced. Moreover, in the manufacturing method of this invention, since it can implement by comparatively low-temperature heat processing, there is no restriction | limiting of a manufacturing apparatus and it can manufacture cheaply.

  Thus, the method of the present invention is an epoch-making method capable of selectively and efficiently producing CNTs having a desired diameter.

The schematic diagram in which an armchair type single-walled CNT is formed from a cycloparaphenylene compound ([n] CPP) in which n paraphenylenes are linked is shown. 2 is a transmission electron micrograph of the CNT obtained in Example 1. 2 is a transmission electron micrograph of the CNT obtained in Example 1. 2 is a graph showing a distribution of diameters measured with a transmission electron microscope of the CNTs obtained in Example 1. The relationship between the excitation wavelength of the laser by the Raman spectroscopy of CNT obtained in Example 1 and a Raman spectrum is shown. The relationship between the excitation wavelength of the laser by the Raman spectroscopy of CNT obtained in Example 2 and a Raman spectrum is shown.

  The CNT production method of the present invention is characterized in that a cyclic compound formed by connecting a plurality of aromatic rings is reacted with a carbon source.

1. Cyclic compound (template) formed by connecting multiple aromatic rings
In the CNT production method of the present invention, a cyclic compound formed by connecting a plurality of aromatic rings can be used as a production raw material. In other words, the cyclic compound can be used as a template (template) for CNT.

  The cyclic compound formed by connecting a plurality of aromatic rings means a compound in which a plurality of aromatic rings are connected in a ring shape while maintaining a π-electron conjugated system. Examples of the cyclic compound formed by connecting aromatic rings include a cyclic compound (carbon nano ring) formed by connecting a plurality of divalent aromatic hydrocarbon groups.

  Examples of the cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups include, for example, a cycloparaphenylene compound and at least one phenylene group of the cycloparaphenylene compound is divalent condensed poly. And modified cycloparaphenylene compounds substituted with a ring aromatic hydrocarbon group.

  Examples of the cycloparaphenylene compound include cycloparaphenylene compounds having 6 or more phenylene groups. Specifically, the general formula (1):

(In the formula, a represents an integer of 6 or more.)
The compound represented by these is mentioned. a is preferably 6 to 100, more preferably 8 to 50, still more preferably 8 to 30, still more preferably 9 to 20, and particularly preferably 10 to 18. Specifically, a includes 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc., and in particular, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 etc. are mentioned.

  The diameter of the ring in the compound represented by the general formula (1) is about 1.2 to 1.7 nm when a is 9 to 12, and 1.8 to 2 when a is 13 to 16. .4 nm, and when a is 13-18, it is about 1.8-2.5 nm.

  In the method for producing CNTs of the present invention, the diameter of the cyclic compound as a starting material is almost transferred to the diameter of the CNTs, so that CNTs having a substantially uniform diameter can be produced.

  The modified cycloparaphenylene compound is a divalent condensed polycyclic ring in which at least one (preferably 1 to 4, more preferably 1 to 2, particularly preferably 1) phenylene group of the above cycloparaphenylene compound is used. It is a compound substituted with an aromatic hydrocarbon group.

  Examples of the divalent condensed polycyclic aromatic hydrocarbon group include two or more (2 to 7, further 2 to 4, such as naphthalene, anthracene, phenanthrene, naphthacene, triphenylene, pyrene, chrysene, pentacene, hexacene, and perylene. And especially a divalent group obtained by removing two hydrogen atoms from a hydrocarbon condensed with a benzene ring. The position of the two bonds of the condensed polycyclic aromatic hydrocarbon group is not particularly limited as long as the modified cycloparaphenylene compound can form a ring.

  As the divalent condensed polycyclic aromatic hydrocarbon group, the general formula (2):

(In the formula, b represents an integer of 1 or more.)
The group represented by these is mentioned. b is preferably an integer of 1 to 6, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

  Specific examples of the cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups include, for example, the general formula (3):

Wherein R ² is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; R ⁴ is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon Group is the same or different, and each is an integer of 0 or more; n is the same or different and each represents an integer of 1 or more.)
Or a cyclic compound represented by the general formula (4):

(In the formula, d represents an integer of 1 or more.)
A cyclic compound represented by the general formula (13):

(Wherein R ⁷ is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; l is 10, 11 or 13)
And the like, and the like.

In the general formula (3), the phenylene groups represented by R ² and R ⁴ may be the same or different, but are preferably 1,4-phenylene groups.

In the general formula (3), the divalent condensed polycyclic aromatic hydrocarbon group represented by R ² and R ⁴ may be the same or different, but two or more (2-7, Furthermore, the bivalent group obtained by remove | excluding two hydrogen atoms from the hydrocarbon which 2-4 (especially 2) benzene rings condensed is mentioned. Specifically, it is as having mentioned above, Preferably group represented by the said General formula (2) is mentioned.

In the general formula (3), m may be the same or different, but is an integer of 0 or more. The integer is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 1 or 2. When m is 2 or more, a plurality of R ⁴ are directly bonded. In this case, R ⁴ directly bonded may be the same or different.

In general formula (3), n may be the same or different, but is an integer of 1 or more. The integer is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 1 or 2. When n is 2 or more, a plurality of R ² are directly bonded. In this case, R ² directly bonded may be the same or different.

In the general formula (3), when at least one of R ² and R ⁴ is a divalent condensed polycyclic aromatic hydrocarbon group (particularly, a group represented by the general formula (2)), Can be. Furthermore, by using this carbon nanoring as a template for the production method of the present invention described later, chiral CNTs that substantially retain the diameter derived from this carbon nanoring can be produced.

  In the general formula (4), d is preferably an integer of 1 to 3, more preferably 1 or 2.

In the general formula (13), as the phenylene group represented by R ⁷ and the divalent condensed polycyclic aromatic hydrocarbon group, specifically, those described as R ² and R ⁴ in the general formula (3) It is the same. The same applies to preferred specific examples. L is 10, 11 or 13.

  That is, as the compound (13), specifically,

It is.

2. Carbon source As the carbon source used in the production method of the present invention, various carbons or carbon-containing compounds can be used. From the template (cyclic compound), a graphene sheet of CNT is grown in the central axis direction of the ring. There is no particular limitation as long as it can be used. For example, carbon, a hydrocarbon compound, an alcohol compound, an ether compound, an ester compound, and the like can be given. One of these or two or more of them can be used.

  Examples of the hydrocarbon compound include saturated or unsaturated aliphatic hydrocarbon compounds and aromatic hydrocarbon compounds.

  Examples of the saturated aliphatic hydrocarbon compound include a linear, branched or cyclic alkane having 1 to 100 (preferably C1 to 10, more preferably C1 to 4). Specific examples include methane, ethane, propane, butane, pentane, hexane, heptane and the like.

  Examples of the unsaturated aliphatic hydrocarbon compound include C2 to 100 (preferably C2 to 10, more preferably C2 to 6) linear, branched or cyclic having 1 to 3 double bonds. Alkenes are mentioned. Specific examples include ethylene, propene, 1-butene, 2-butene, butadiene and the like, preferably ethylene. Or the linear or branched alkyne of C2-100 (preferably C2-10, more preferably C2-4) which has 1-3 triple bonds is mentioned. Specific examples include acetylene and propyne, and acetylene is preferred.

  Examples of the aromatic hydrocarbon compound include monocyclic or polycyclic aromatic hydrocarbons, and specifically include benzene, toluene, xylene, naphthalene, cumene, ethylbenzene, phenanthrene, anthracene, and the like.

  Examples of the alcohol compound include C1-50 (preferably C1-10, more preferably C1-4) linear, branched, or cyclic mono- or polyalcohol. Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, ethylene glycol and the like. Preferred are methanol, ethanol, propanol and the like.

  Examples of ether compounds include C2-50 (preferably C2-10, more preferably C2-4) linear, branched or cyclic ethers. Specific examples include dimethyl ether, diethyl ether, diisopropyl ether, diisobutyl ether, tetrahydrofuran, dioxane and the like.

Examples of the ester compound include the formula: R ⁵ —C (═O) O—R ⁶ (wherein R ⁵ represents a hydrogen atom or a C 1-10 alkyl group. R ⁶ represents a C 1-10 alkyl group. The compound represented by this is shown. The C1-10 alkyl group represented by R ⁵ and R ⁶ may be the same or different, and may be a straight chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or the like. A branched alkyl group is exemplified. Specific examples include methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate and the like.

  In consideration of the production method of the present invention, a carbon source that can become a gas under reduced pressure is preferable, for example, C1-6 linear, branched or cyclic monoalcohol such as methanol, ethanol, propanol, etc .; methane C1-6 linear, branched or cyclic alkane such as ethane; C2-4 alkene such as ethylene; C2-4 alkyne such as acetylene, and the like are preferable.

3. CNT Production Method The CNT production method of the present invention is characterized in that a cyclic compound (template) formed by linking a plurality of aromatic rings is reacted with a carbon source. Specifically, it is preferable to supply a gaseous carbon source and heat under reduced pressure. The production method of the present invention can be carried out, for example, by chemical vapor deposition (CVD) in the presence of a carbon source using the cyclic compound as a template. Typically, a CNT is produced by placing a template on a suitable carrier and subjecting the template to chemical vapor deposition (CVD) using a source gas containing a carbon source under reduced pressure and heating conditions. Can do. In the production method of the present invention, a CNT can be produced by expanding a graphene sheet from a template (expanding a π-electron conjugated system) without using a catalyst (metal catalyst or the like) used in a conventional CVD method. (See, for example, FIG. 1). The obtained CNTs are single-walled CNTs (SWCNTs).

  The carrier for placing the template is not particularly limited as long as it is a material that can carry the template and does not adversely affect the process of producing CNTs. For example, silica, alumina, magnesia, ceria, porous zeolite, mesoporous silica, etc. Can be mentioned. The shape of the carrier is not particularly limited, and examples thereof include various shapes such as powder, particles, and flat plate.

  Further, a substrate may be used as the carrier. Examples of the substrate include a sapphire single crystal substrate, a silicon substrate, a quartz glass substrate, a porous silicon substrate, and a porous alumina substrate, and a sapphire single crystal substrate is preferable. The method for disposing the template on the substrate is not particularly limited. For example, the template can be disposed by coating the substrate with a solution obtained by dissolving the template in an appropriate solvent.

  The solvent is not particularly limited as long as it can dissolve the template. For example, alcohols (for example, methanol, ethanol, propanol, etc.), ethers (for example, diethyl ether, tetrahydrofuran, dioxane, etc.), aromatic carbonization, etc. Examples thereof include hydrogens (for example, benzene, toluene, xylene and the like), esters (for example, ethyl acetate and the like), and the like. The concentration of the solution containing the template can be appropriately changed depending on the solubility of the template, the size of the substrate, and the like. Usually, the concentration is preferably low so that the template molecules can be arranged in a single molecule state without overlapping on the substrate. For example, 0.00001-0.01 weight%, Preferably 0.0001-0.005 weight% is mentioned.

  The method for coating the solution containing the template on the substrate is not particularly limited, and examples thereof include spin coating, spray coating, dip coating, and the like, preferably spin coating. When spin coating is used, the number of rotations is, for example, about 1000 to 10,000 rpm, and the rotation time is about 10 to 30 seconds. The template can then be placed on the substrate by drying and removing the solvent.

  It is preferable that the support on which the template is arranged is transferred to a reactor and subjected to a CVD method using a carbon source. Usually, the reaction is carried out at an appropriate temperature and pressure after evacuating the reactor containing the carrier and supplying or supplying a gas containing a carbon source. The reaction is preferably carried out while stabilizing the temperature, pressure, and supply amount of the carbon source.

  The atmosphere gas for the reaction is not particularly limited as long as it does not react with the template or CNT under the reaction conditions and is inactive, and examples thereof include helium, argon, hydrogen, nitrogen, neon, krypton, or a mixed gas thereof. . In particular, helium, argon and the like are preferable.

  In general, the carbon source can be supplied in a gaseous form. The supply amount of the carbon source is not particularly limited, and in the case of a gaseous carbon source, it may normally be 5 to 2000 mL / min. Alternatively, a mixed gas diluted with a gaseous carbon source and the above atmospheric gas may be supplied.

The pressure in the reactor is usually preferably under reduced pressure (atmospheric pressure or less), for example, about 10 ⁻⁴ to 10 ⁵ Pa, preferably about 10 ⁻³ to 10 ⁵ Pa, more preferably 10 ² to 10 ⁴ Pa. Degree.

  The temperature in the reactor is usually 400 to 1200 ° C, preferably 450 to 700 ° C, more preferably 450 to 500 ° C. The reaction time is, for example, 5 to 30 minutes, preferably 10 to 15 minutes.

  The structure of the obtained CNT can be evaluated by Raman spectroscopy and transmission electron microscope (TEM) observation.

  Further, in the TEM, from the TEM image of the single-walled carbon nanotube, it is possible to confirm the diameter of the CNT, the single-walled CNT forming a bundle, the presence or absence of defects on the wall surface of the single-walled carbon nanotube, and the like. For example, FIG. 4 shows the result of the CNT diameter distribution measured with a transmission electron microscope for the CNT produced from [12] cycloparaphenylene in Example 1.

  In Raman spectroscopy, a vibration mode called a breathing mode appears when one graphene sheet is seamlessly wound into a cylindrical shape. Since it is known that the frequency of this vibration mode is inversely proportional to the diameter of the tube, the distribution of the diameter of the CNT can be known by measuring the frequency of the breathing mode by Raman scattering.

  In Raman spectroscopy, the ratio of the spectral intensity of the G band, which is a Raman band unique to CNT, and the intensity of the spectrum of the D band derived from amorphous carbon (G / D ratio) is used to determine the purity of the single-walled carbon nanotube after synthesis. Can be used as an index (a scale representing the degree of impurity contamination).

  In Raman spectroscopy, since the detected CNT differs depending on the wavelength of the laser used, the physical properties of the CNT can be evaluated using lasers having different wavelengths. As for the CNT obtained by the method of the present invention, for example, semiconductor CNT is detected at laser excitation wavelengths of 514 nm and 488 nm, and metal CNT is detected at an excitation wavelength of 633 nm.

  The production method of the present invention can produce CNTs that reproduce the diameter of the cyclic compound of the template almost faithfully. Therefore, it has a feature that the distribution of diameter is extremely small as compared with CNTs manufactured by a conventional general CVD method. For example, in Example 1, when [12] cycloparaphenylene (ring diameter: 1.65 nm) in which 12 phenylene groups are linked is used as a template, the obtained CNT has a diameter of 1.4 to 1.6 nm. [12] It almost coincides with that of CPP (FIG. 4). Therefore, the production method of the present invention is useful as a method for producing CNTs with a controlled diameter using a template.

  Moreover, the production method of the present invention does not require a catalyst or a high temperature, and can be carried out under relatively low conditions. This is presumably because a graphene sheet can be formed (pi-conjugated system grows) under milder conditions without using a catalyst or high temperature because a template is used as a starting material.

  Moreover, in the manufacturing method of this invention, since it is not necessary to use catalysts, such as a metal catalyst, the obtained CNT does not contain the impurity derived from a catalyst. Therefore, high-purity CNT can be obtained without going through a troublesome purification process. In addition, since the metal fine particles of the catalyst are not included, the obtained CNTs can be used without problems in applications such as devices, transistors, integrated circuits, memories, sensors, and wiring.

4). Cyclic compounds more aromatic rings formed by connecting used as a template in the method for manufacturing a template for manufacturing the present invention can be prepared, for example, in the following manner.

  The cycloparaphenylene compound (particularly, the compound represented by the general formula (1)) can be produced, for example, according to or according to the methods described in Non-Patent Documents 1 to 4. Carbon nanorings (cycloparaphenylene compounds and / or modified cycloparaphenylene compounds) can also be produced, for example, by the production methods shown in Reaction Formulas 1 to 3.

  <Reaction Formula 1>

(Wherein R ¹ is the same or different and each represents a hydrogen atom or hydroxyl protecting group; R ² is the same or different and each represents a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; is R ⁴ the same? Or different, each phenylene group or divalent condensed polycyclic aromatic hydrocarbon group; m ′ is the same or different, each is an integer of 1 or more; n is the same or different, each is an integer of 1 or more; is X the same? Or different, each halogen atom; Y is the same or different and each has the general formula (9):

(Wherein, ^{R 3} are identical or different, are each a hydrogen atom or an alkyl group C1-10, ^{R 3} may form a ring -O-B-O- with the adjacent bonded to each other. )
The group shown by is shown. )

R ¹ is a hydrogen atom or a protecting group for a hydroxyl group. Examples of the hydroxyl-protecting group include an alkoxyalkyl group (for example, methoxymethyl group (—CH ₂ —O—CH ₃ , hereinafter sometimes referred to as “-MOM”)), an alkanoyl group (for example, acetyl group). Group, propionyl group etc.), silyl group (eg trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group etc.), tetrahydropyranyl group (THP), alkyl group (eg methyl group, ethyl group etc.), aralkyl Group (for example, benzyl group etc.) etc. are mentioned, Preferably it is an alkoxyalkyl group, especially a methoxymethyl group.

R ² and R ⁴ are as described above.

  m ′ is preferably an integer of 1 to 30, more preferably an integer of 1 to 20, still more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 2.

  n is as described above.

  Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A bromine atom and an iodine atom are preferable, and a bromine atom is particularly preferable.

In the monovalent group represented by the general formula (9) represented by Y (hereinafter referred to as “boronic acid or its ester group”), the alkyl group represented by R ³ is preferably C1-8. And more preferably a C1-5 alkyl group, which may be linear or branched. When R ³ is an alkyl group, the carbon atoms constituting each alkyl group may be bonded to each other to form a ring together with a boron atom and two oxygen atoms. In this case, as Y, for example, the following formulas (9a) to (9c):

It can be set as group shown by these. When Y in the compound (6) is a group represented by the above formulas (9a) to (9c), the reaction between the compound (5) and the compound (6) can proceed more efficiently.

Compounds (5) and (6):
Compounds (5) and (6) can be synthesized in accordance with Non-patent Document 3, Synthesis Examples 1 to 5 of the present specification or the like.

Synthesis of compound (7a):
Compound (7a) can be produced by reacting compound (5) with compound (6). For the reaction between the compound (5) and the compound (6), a Suzuki-Miyaura coupling reaction can be used. The Suzuki-Miyaura coupling reaction is a carbon-carbon bond reaction, and is a reaction in which an aryl halide compound and an organic boron compound are coupled. The compound (5) is a halogenated aryl compound having a halogen atom, and the compound (6) is an organoboron compound having a boronic acid or an ester group thereof.

  The amount of compound (6) used in the above reaction is preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.4 mol, still more preferably 0. It is 08-0.2 mol.

In the above reaction, a palladium catalyst is usually used. Examples of the palladium-based catalyst include Pd (PPh ₃ ) ₄ (Ph is a phenyl group), PdCl ₂ (PPh ₃ ) ₂ (Ph is a phenyl group), Pd (OAc) ₂ (Ac is an acetyl group), Tris ( Dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ), tris (dibenzylideneacetone) dipalladium (0) chloroform complex, bis (dibenzylideneacetone) palladium (0), bis (tri-t-butylphosphine) Fino) palladium (0), (1,1′-bis (diphenylphosphino) ferrocene) dichloropalladium (II), and the like. In this step, Pd (PPh ₃ ) ₄ , Pd ₂ (dba) _{3 and the} like are preferable.

  From the viewpoint of yield, the amount of the palladium-based catalyst is usually 0.0001 to 0.1 mol, preferably 0.0005 to 0.02 mol, relative to 1 mol of the compound (5) as a raw material. Preferably it is 0.001-0.01 mol.

  In the above reaction, a phosphorus ligand capable of coordinating with a palladium atom which is a central element of the palladium-based catalyst can be used as necessary. Examples of the phosphorus ligand include triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris (2,6-dimethoxyphenyl) phosphine, tris [2- (Diphenylphosphino) ethyl] phosphine, bis (2-methoxyphenyl) phenylphosphine, 2- (di-t-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) biphenyl, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, tri-t-butylphosphine, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (dimethylphosphino) ethane 1,3-bis (diphenylphosphino) propane, 1,4-bis ( Phenylphosphino) butane, 1,5-bis (diphenylphosphino) pentane, 1,6-bis (diphenylphosphino) hexane, 1,2-bis (dimethylphosphino) ethane, 1,1′-bis (diphenyl) Phosphino) ferrocene, bis (2-diphenylphosphinoethyl) phenylphosphine, 2- (dicyclohexylphosphino-2 ′, 6′-dimethoxy-1,1′-biphenyl (S-Phos), 2- (dicyclohexylphosphino) -2 ′, 4 ′, 6′-tri-isopropyl-1,1′-biphenyl (X-Phos), bis (2-diphenylphosphinophenyl) ether (DPEPhos), etc. In this step, 2- (Dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl X-Phos), and the like are preferable.

  When using a phosphorus ligand, the usage-amount is 0.001-1.0 mol normally with respect to 1 mol of said compounds (5) of a raw material from a viewpoint of a yield, Preferably 0.01- 0.8 mol, more preferably 0.05 to 0.3 mol.

  In the above reaction, it is preferable to add a base (boron atom activator) in addition to the palladium catalyst. The base is not particularly limited as long as it is a compound that can form an art complex on a boron atom in the Suzuki-Miyaura coupling reaction. Specifically, for example, potassium fluoride, cesium fluoride, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium acetate , Potassium acetate, calcium acetate and the like. Of these, cesium fluoride, cesium carbonate, and potassium phosphate are preferred. The amount of the base used is usually 0.01 to 10 mol, preferably 0.1 to 5.0 mol, more preferably 0.5 to 1.0 mol, per 1 mol of the raw material compound (5). It is.

  The coupling reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbons such as toluene, xylene, and benzene; esters such as methyl acetate, ethyl acetate, and butyl acetate; cyclic ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and diisopropyl ether; Halogenated hydrocarbons such as methyl chloride, chloroform, dichloromethane, dichloroethane, dibromoethane; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile; methanol, ethanol, isopropyl alcohol, and the like Alcohols; dimethyl sulfoxide and the like. These may be used alone or in combination of two or more. Of these, tetrahydrofuran is preferred in the present invention.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent. The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

  After the reaction, a purification step can be provided as necessary. In this purification step, it can be subjected to general post-treatment such as solvent (solvent) removal, washing, chromatographic separation and the like.

According to the above production method, the number of aromatic rings of the compound (7a), that is, the length of the molecule can be designed freely and accurately by appropriately selecting the number n of R ² in the compound (6). Can do.

Synthesis of compound (8):
This reaction may be referred to as a compound (7a) and a boron compound having boronic acid or an ester group thereof (—B (OR ³ ) ₂ ; R ³ is the same as above) (hereinafter simply referred to as “boron compound”). ) To form a compound (8).

  In this reaction, the halogen atom X contained in the compound (7a) is substituted with a boronic acid or its ester group Y contained in the boron compound. As a result, a boronic acid-derived boronic acid or a compound (8) having an ester group Y thereof is formed. The reaction to form this compound (8) is a borylation reaction.

  Specific examples of the boron compound used in the above reaction include 2-phenyl-1,3,2-dioxaborinane, (4,4,5,5) -tetramethyl-1,3,2-dioxaborolane, 4 4,4 ′, 4 ′, 5,5,5 ′, 5′-octamethyl-2,2′-bi [1,3,2-dioxaborolane] (bispinacolatodiboron), 5,5,5 ′ , 5′-tetramethyl-5,5 ′, 6,6′-tetrahydro-2,2′-bi [4H-1,3,2-dioxaborin], 1,1,2,2-tetrahydroxy-1, 2-Diboraethane etc. are mentioned.

  The amount of the boron compound used in the above reaction is preferably 1 to 10 mol, more preferably 1.5 to 7 mol, and still more preferably 2 to 5 mol, per 1 mol of compound (7a). .

The above reaction is usually carried out in the presence of a catalyst, and preferably a palladium catalyst is used. As the palladium-based catalyst, the palladium-based catalyst shown in the description of the coupling reaction can be used. In particular, Pd ₂ (dba) ₃ , Pd (PPh ₃ ) _{4 and the} like are preferable.

  When using a palladium-based catalyst, the amount used is usually 0.001 to 1 mol, preferably 0.005 to 0.1 mol, relative to 1 mol of the starting compound (7a), from the viewpoint of yield. More preferably, it is 0.01-0.05 mol.

  In this reaction, a phosphorus ligand can be used together with the catalyst. As the phosphorus ligand, those shown in the description of the coupling reaction can be used. In particular, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.

  When a phosphorus ligand is used, the amount used is generally 0.01 to 1.0 mol, preferably 0.05 to 0, relative to 1 mol of the starting compound (7a) from the viewpoint of yield. 0.5 mol, more preferably 0.08 to 0.2 mol.

  In this reaction, a base may be used as necessary. As the base to be used, the base shown in the description of the coupling reaction can be used. The amount of the base used is usually about 0.1 to 5.0 mol, preferably 0.5 to 1.0 mol, per 1 mol of the starting compound (7a).

  This reaction is usually performed in the presence of a reaction solvent. As the reaction solvent, those shown in the above description of the coupling reaction can be used.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent. The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

  When the boron compound is a compound having a cyclic boronic acid ester group, it may be hydrolyzed and converted to a boronic acid group after producing the compound (8) having the boronic acid ester group.

Synthesis of compound (7b):
This step is a step of forming compound (7b) from compound (8) and compound (10).

In this step, the boronic acid or its ester group Y contained in the compound (8) is substituted with — [R ⁴ ] _{m ′} —X. Thereby, the magnitude | size of a carbon nanoring can be adjusted suitably.

  The amount of compound (10) to be used is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, further preferably 0.8 to 2 mol, per 1 mol of compound (8). Is a mole.

This reaction is usually performed in the presence of a catalyst, and a palladium-based catalyst is preferably used. As the palladium-based catalyst, the palladium-based catalyst shown in the description of the coupling reaction can be used. In particular, (1,1′-bis (diphenylphosphino) ferrocene) dichloropalladium (II), Pd ₂ (dba) ₃ , Pd (PPh ₃ ) _{4 and the} like are preferable.

  When using a palladium catalyst, the amount used is usually 0.001 to 1 mol, preferably 0.005 to 0.2 mol, relative to 1 mol of the starting compound (8), from the viewpoint of yield. More preferably, it is 0.01-0.1 mol.

  A phosphorus ligand can be used together with the catalyst. As the phosphorus ligand, those shown in the description of the coupling reaction can be used. In particular, 1,1′-bis (diphenylphosphino) ferrocene, 2- (dicyclohexylphosphino) -2 ′, 4 ′, 6′-tri-isopropyl-1,1′-biphenyl (X-Phos) and the like are preferable. .

  When a phosphorus ligand is used, the amount used is generally 0.01 to 1.0 mol, preferably 0.05 to 0, relative to 1 mol of the starting compound (8) from the viewpoint of yield. 0.5 mol, more preferably 0.08 to 0.2 mol.

  In this reaction, a base may be used as necessary. As the base to be used, the base shown in the description of the coupling reaction can be used. Preferred bases are sodium carbonate, potassium phosphate and the like. The amount of the base to be used is generally about 0.1 to 5.0 mol, preferably 0.5 to 1.0 mol, per 1 mol of the raw material compound (8).

  This reaction is usually performed in the presence of a reaction solvent. As the reaction solvent, those shown in the above description of the coupling reaction can be used. In this step, toluene, 1,4-dioxane, water, a mixed solvent thereof and the like are preferable.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent. The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

  <Reaction Formula 2>

(Wherein R ¹ , R ² , R ⁴ , m, n, X and Y are the same as above)

Synthesis of Compound (11) from Compounds (7) and (8):
This step is a step of forming the compound (11) from the compound (7) and the compound (8). Here, the compound (7) is a compound obtained by combining the compound (7a) and the compound (7b).

  Compound (11) can be obtained through a coupling step in which compound (7) and compound (8) are subjected to a coupling reaction to form a ring-shaped compound. Since both compound (7) and compound (8) have a U-shaped shape, compound (11) can be obtained efficiently.

  In the coupling reaction, the amount of compound (8) used is preferably 0.8 to 3.0 mol, more preferably 1.0 to 2.0 mol, relative to 1 mol of compound (7). More preferably, it is 1.2-1.8 mol.

This reaction is usually performed in the presence of a catalyst, and a palladium-based catalyst is preferably used. As the palladium-based catalyst, the palladium-based catalyst shown in the description of the coupling reaction can be used. In particular, Pd ₂ (dba) ₃ , Pd (PPh ₃ ) _{4 and the} like are preferable.

  In the case of using a palladium-based catalyst, the amount used is usually 0.001 to 1 mol, preferably 0.005 to 0.1 mol, based on 1 mol of the starting compound (7), from the viewpoint of yield. More preferably, it is 0.01-0.05 mol.

  A phosphorus ligand can be used together with the catalyst. As the phosphorus ligand, those shown in the description of the coupling reaction can be used. In particular, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.

  When a phosphorus ligand is used, the amount used is usually 0.01 to 1.0 mol, preferably 0.05 to 0, relative to 1 mol of the starting compound (7) from the viewpoint of yield. 0.5 mol, more preferably 0.08 to 0.2 mol.

  In this reaction, a base may be used as necessary. As the base to be used, the base shown in the description of the coupling reaction can be used. Preferred bases are cesium fluoride, cesium carbonate, potassium phosphate and the like. The amount of the base used is usually about 0.1 to 5.0 mol, preferably 0.5 to 1.0 mol, per 1 mol of the starting compound (7).

  This reaction is usually performed in the presence of a reaction solvent. As the reaction solvent, those shown in the above description of the coupling reaction can be used. In this reaction, tetrahydrofuran or the like is preferable.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent. The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

Synthesis of cyclic compound (3) from compound (11):
The cyclic compound (3) is obtained by converting the cyclohexane ring part of the compound (11) into a benzene ring (aromatic cyclization).

For this reaction, for example, a general oxidation reaction may be performed. Specific examples thereof include, for example, a method of heating (acid treatment) compound (11) in the presence of an acid, a method of heating in the presence of oxygen (air atmosphere, oxygen atmosphere, etc.), quinones, and metal oxidizer. The method of making it react with etc. is also mentioned. Thereby, dehydrogenation reaction etc. are applied normally and the cyclohexane ring part which compound (11) has can be chemically changed to a benzene ring (aromatic cyclization), and a cyclic compound (3) is compoundable. That is, OR ¹ in the cyclohexane ring part of the ring-shaped compound before conversion is also eliminated, and the dehydrogenation reaction proceeds to obtain the cyclic compound (3).

In the case of performing the acid treatment, the specific method and the like are not particularly limited. For example, the following method and the like are preferable.
(A) A method in which the compound (11) and an acid are dissolved in a solvent, and then the obtained solution is heated and reacted.
(B) A method in which the compound (11) is dissolved in a solvent, and then the mixture obtained by mixing the resulting solution and an acid is heated and reacted.

  In addition, when performing the said reaction, it can also be set as the acid treatment by a non-solvent.

  Although an acid is not specifically limited, The strong acid used for a catalyst etc. is preferable. Examples thereof include sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, molybdosilicic acid, boron trifluoride ethylate, and tin tetrachloride. These can be used alone or in combination of two or more.

  Although the amount of the acid used varies depending on the production conditions and the like, in the case of the above method (A), 0.01 to 100 mol is preferable and 0.5 to 50 mol equivalent is more preferable with respect to 1 mol of compound (11). 1 to 20 mol is more preferable.

  In the case of the method (B), the amount of acid used is preferably 0.01 to 100 mol, more preferably 0.5 to 50 mol, and more preferably 1 to 20 mol, relative to 1 mol of compound (11). The equivalent is more preferable.

  The solvent used for the acid treatment reaction may be a nonpolar solvent or a polar solvent. For example, alkanes such as hexane, heptane, and octane; haloalkanes such as methylene chloride, chloroform, carbon tetrachloride, and ethylene chloride; benzenes such as benzene, toluene, xylene, mesitylene, and pentamethylbenzene; chlorobenzene, bromobenzene, and the like Halobenzenes; ethers such as diethyl ether and anisole; dimethyl sulfoxide and the like. The said solvent can be used individually by 1 type or in combination of 2 or more types.

  In the case of using a solvent, the reaction intermediate from the raw material to the cyclic compound (3) may have low solubility in one solvent used. In this case, the other solvent is used in advance or It may be added in the middle of the reaction.

  Although the usage-amount in the case of using a solvent is suitably selected by manufacturing conditions etc., 100-100000 mass parts is preferable with respect to 100 mass parts of compounds (11), and 1000-10000 mass parts is more preferable.

  The heating temperature in the methods (A) to (B) is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. When using a solvent, it selects from the range below the boiling point temperature of the said solvent.

  Examples of the heating means include an oil bath, an aluminum block thermostat, a heat gun, a burner, and microwave irradiation. In the case of irradiation with microwaves, a known microwave reaction apparatus used for microwave reaction can be used. In heating, reflux cooling may be used in combination.

  The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

  After the reaction, a purification step can be provided as necessary. That is, it can be subjected to general post-treatment such as solvent (solvent) removal (when a solvent is used), washing, chromatographic separation, and the like. Since the obtained cyclic compound (3) is usually amorphous (non-crystalline), it can be crystallized using a known recrystallization method. In the crystallized product, the organic solvent used in the recrystallization operation may be included in the ring constituting the molecule.

  In the above reaction formula, by appropriately adjusting the numbers of m and n, a cyclic compound in which 14 or more divalent aromatic rings are linked can be obtained. For example, in the case of a compound in which both m is 0 and n is 1, a cyclic compound in which 14 divalent aromatic rings are connected can be obtained. In the case of a compound in which m is 1 and 0 and n is 1, a cyclic compound in which 15 divalent aromatic rings are connected can be obtained. Further, in the case of a compound in which both m is 1 and n is 1, a cyclic compound in which 16 divalent aromatic rings are connected can be obtained.

  <Reaction Formula 3>

(In the formula, d represents an integer of 1 or more. R ¹ and X are the same as above.)

Synthesis of compound (12):
In this reaction, a plurality of compounds (5) are combined (homocoupled) to form a ring-shaped compound (12). Compound (5) has two halogen atoms, and by using a nickel compound, the carbon atoms to which the halogen atoms are bonded, that is, the carbon bonded to the halogen atoms in one compound (5). An atom and the carbon atom couple | bonded with the halogen atom in another compound (5) can be combined. Thereby, the coupling reaction of the compounds (5) can be continuously carried out, and the carbon atoms can be bonded to each other to obtain the ring-shaped compound (12).

  Compound (5) is bonded to a benzene ring at two positions, 1-position and 4-position, and this benzene ring is in an axial or equatorial arrangement, thereby forming a compound having an L-shaped structure. Can do. By using a compound having a structure such as an L-shaped structure as the compound (5), formation of the compound (12) having a ring structure can be facilitated.

  In this reaction, a nickel compound is usually used. The nickel compound is not particularly limited, but a zero-valent Ni salt or a divalent Ni salt is preferable. These can be used alone or in combination of two or more. These complexes mean both those charged as reagents and those produced in the reaction.

  The zero-valent Ni salt is not particularly limited, and examples thereof include bis (1,5-cyclooctadiene) nickel (0), bis (triphenylphosphine) nickel dicarbonyl, nickel carbonyl and the like.

  Examples of the divalent Ni salt include nickel acetate (II), nickel trifluoroacetate (II), nickel nitrate (II), nickel chloride (II), nickel bromide (II), nickel (II) acetyl. Acetonate, nickel (II) perchlorate, nickel (II) citrate, nickel (II) oxalate, nickel (II) cyclohexanebutyrate, nickel (II) benzoate, nickel (II) stearate, nickel stearate ( II), sulfamine nickel (II), nickel carbonate (II), nickel thiocyanate (II), nickel trifluoromethanesulfonate (II), bis (1,5-cyclooctadiene) nickel (II), bis (4- Diethylaminodithiobenzyl) nickel (II), nickel (II) cyanide, difluoride Kell (II), nickel boride (II), nickel borate (II), nickel hypophosphite (II), ammonium nickel sulfate (II), nickel hydroxide (II), cyclopentadienyl nickel (II), And hydrates thereof, and mixtures thereof.

  As the zero-valent Ni salt and the divalent Ni salt, a compound in which a ligand is coordinated in advance may be used.

  The amount of nickel compound used is usually 0.01 to 50 mol, preferably 0.1 to 10 mol, more preferably 0.1 to 10 mol, based on 1 mol of the starting compound (5). It is 0.5-5 mol, Most preferably, it is 1-3 mol.

  In this reaction, a ligand capable of coordinating to nickel (nickel atom) can be used together with the nickel compound. Examples of the ligand include carboxylic acid, amide, phosphine, oxime, sulfonic acid, 1,3-diketone, Schiff base, oxazoline, diamine, carbon monoxide, and carbene. And a ligand. These can be used alone or in combination of two or more. Coordination atoms in the above ligand are a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, and the like. These ligands include a monodentate ligand having only one coordination atom and a polydentate having two or more. There are bidentate ligands. In addition, carbon monoxide and carbene are ligands having a carbon atom as a coordination atom.

  Monodentate ligands include triphenylphosphine, trimethoxyphosphine, triethylphosphine, tri (i-propyl) phosphine, tri (tert-butyl) phosphine, tri (n-butyl) phosphine, tri (isopropoxy) phosphine, Tri (cyclopentyl) phosphine, tri (cyclohexyl) phosphine, tri (ortho-tolyl) phosphine, tri (mesityl) phosphine, tri (phenoxy) phosphine, tri- (2-furyl) phosphine, bis (p-sulfonate phenyl) phenyl Examples include phosphine potassium, di (tert-butyl) methylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, triethylamine, and pyridine.

  Bidentate ligands include 2,2'-bipyridyl, 4,4 '-(tert-butyl) bipyridyl, phenanthroline, 2,2'-bipyrimidyl, 1,4-diazabicyclo [2,2,2] octane 2- (dimethylamino) ethanol, tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, 2-aminomethylpyridine, or (NE) -N- (pyridin-2-ylmethylidene) aniline, 1,1′-bis (diphenylphosphino) ferrocene, 1,1′-bis (tert-butyl) ferrocene, diphenylphosphinomethane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenyl) Phosphino) propane, 1,5-bis (diphenylphosphino) pentane, 1,2-bis Dipentafluorophenylphosphino) ethane, 1,2-bis (dicyclohexylphosphino) ethane, 1,3- (dicyclohexylphosphino) propane, 1,2-bis (di-tert-butylphosphino) ethane, 1, 3-bis (di-tert-butylphosphino) propane, 1,2-bis (diphenylphosphino) benzene, 1,5-cyclooctadiene, BINAP, BIPHEMP, PROPHOS, DIOP, DEGUPHOS, DIPAMP, DuPHOS, NORPHOS, PNNP, SKEWPHOS, BPPFA, SEGPHOS, CHIRAPHOS, JOSIPHOS, etc., and mixtures thereof. In addition, the BINAP includes a BINAP derivative, and the BIPHEM includes the BIPHEM derivative.

  When a ligand is used, the amount used is usually 0.01 to 50 mol, preferably 0.1 to 10 mol, more preferably 0.5 to 1 mol, relative to 1 mol of the starting compound (5). 5 mol, particularly preferably 1 to 3 mol.

  The above reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include aliphatic hydrocarbons (hexane, cyclohexane, heptane, etc.), aliphatic halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, dichloroethane, etc.), aromatic hydrocarbons (benzene, toluene, Xylene, chlorobenzene, etc.), ethers (diethyl ether, dibutyl ether, dimethoxyethane (DME), cyclopentyl methyl ether (CPME), tert-butyl methyl ether, tetrahydrofuran, dioxane, etc.), esters (ethyl acetate, ethyl propionate, etc.) ), Acid amides (dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (1-methyl-2-pyrrolidinone) (NMP), nitriles (acetonitrile, propionitrile, etc.), dimethyl Sulfoxide (DMSO) and the like. They may be used in combination of at least one kind alone or two kinds.

  The amount of the solvent in the reaction is usually 1 to 1000 parts by mass, preferably 5 to 200 parts by mass, and more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the compound (5) as a raw material.

  The reaction temperature in the above reaction is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.

Synthesis of compound (4):
The conversion from the compound (12) to the compound (4) can be carried out in the same manner as the method for converting from the compound (11) to the compound (3) in the above <Reaction formula 2>.

  In the above reaction formula, for example, in the case of a compound where d is 1, a cyclic compound in which nine divalent aromatic rings are connected can be obtained. In the case of a compound in which d is 2, a cyclic compound in which twelve divalent aromatic rings are connected can be obtained.

  By the method described above, a cyclic compound in which 9, 12, or 14 or more divalent aromatic rings are linked can be obtained. In addition, as the compound (13), the general formula (13):

(Wherein R ⁷ is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; l is 10, 11 or 13)
It is also possible to synthesize a cyclic compound represented by

  In this method, a cyclic compound in which various numbers of divalent aromatic rings are linked can be obtained by employing the following methods 1, 2 and the like using the raw materials shown below. In addition, this method is a method including the method of using the above reaction formulas 1-3.

<Raw material>
Here, as a raw material, general formula (I):

(Wherein R ¹ is the same as above; Y ′ is the same or different, and each is a halogen atom, or a boronic acid or an ester group thereof.)
And a compound represented by the general formula (II):

(In the formula, Y ′ is the same as above.)
As a raw material, a compound obtained by reacting one compound selected from the group consisting of the compounds represented by the above or two or more compounds is used.

  More preferably, compound (5), general formula (Ib):

(In the formula, R ¹ and Y are the same as above.)
A compound represented by formula (10), and compound (6):
By using a combination of various compounds and reactions capable of producing a cyclic compound by using one compound selected from the group consisting of, or a compound obtained by reacting two or more compounds, a cyclic compound is obtained. A compound can be obtained.

  In addition, as above-mentioned, the method using Reaction formula 1-3 is this example.

  The halogen atom (indicated by Y ′) is not particularly limited. Specifically, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. In the present invention, a bromine atom and an iodine atom are preferable, and a bromine atom is particularly preferable. Y ′ (when Y ′ is a halogen atom) may be the same or different.

  The boronic acid or its ester group (indicated by Y or Y ′) is as described above.

  Compound (Ib) can be obtained by converting halogen atoms at both ends of compound (5) into boronic acid or an ester group thereof by, for example, a borylation reaction using a boron compound.

  Examples of the boron compound include those described above.

  1-10 mol is preferable with respect to 1 mol of compounds (5), and, as for the usage-amount of a boron compound, 1.5-7 mol is more preferable.

The reaction is usually performed in the presence of a catalyst, and a palladium-based catalyst is preferably used. As this palladium-type catalyst, what was demonstrated by the method using the said Reaction formulas 1-3 is mentioned. In this step, Pd ₂ (dba) ₃ , Pd (PPh ₃ ) ₄ , (1,1′-bis (diphenylphosphino) ferrocene) dichloropalladium (II) and the like are preferable.

  In the case of using a palladium-based catalyst in this step, the amount used is usually preferably 0.001 to 1 mol, preferably 0.005 to 0.005 mol per mol of the raw material compound (5) from the viewpoint of yield. 1 mole is more preferred.

  Moreover, if necessary, a phosphorus ligand that can be coordinated to a palladium atom that is a central element of the palladium-based catalyst can be used together with the catalyst. As this phosphorus ligand, what was demonstrated by the method using the said Reaction formulas 1-3 is mentioned. In this step, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.

  When a phosphorus ligand is used, the amount used is preferably 0.01 to 1.0 mol, preferably 0.05 to 0, relative to 1 mol of the starting compound (5) from the viewpoint of yield. More preferred is 5 moles.

  In addition to the palladium catalyst, a base (boron atom activator) may be used as necessary. Examples of the base include those described in the method using the above reaction formulas 1 to 3. Of these, potassium acetate is preferred. The amount of the base used is usually preferably about 0.1 to 5.0 mol, more preferably 0.5 to 1.0 mol, per 1 mol of the raw material compound (5).

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include those described in the method using the above reaction formulas 1 to 3. Of these, dimethyl sulfoxide and the like are preferable in this step.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.

  The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

  In addition, when a boron compound is a compound which has a cyclic boronic ester group, after manufacturing the compound which has this boronic ester group, it may hydrolyze and may convert into a boronic acid group.

  Of the compounds used as raw materials, compounds obtained by reacting two or more compounds of compound (I) and compound (II) include, for example, general formula (14):

(Wherein R ¹ and Y ′ are the same as above).
A compound represented by
Formula (15):

(In the formula, R ¹ , R ² , Y ′ and n are the same as above.)
A compound represented by formula (7a), compound (8), general formula (16):

(Wherein R ⁸ is the same as R ² or R ⁴ ; m1 is the same as n or m ′; Y ′ is the same as above.)
And the like.

Compound (14)
Compound (14) can be obtained, for example, by a reaction using compound (I). More specifically, using the compound (5) and the compound (Ib), the terminal halogen atom of the compound (5) is reacted with the boronic acid at the terminal of the compound (Ib) compound or its ester group. The compound (14) is obtained by trimerization.

(Wherein R ¹ , X, Y and Y ′ are the same as above).
In this reaction, the compound (14) can be obtained as a C-shaped chain compound by utilizing the bent portion of the cyclohexane ring.

  For the reaction between the compound (5) and the compound (Ib), a Suzuki-Miyaura coupling reaction can be used.

  It is preferable to adjust the usage-amount of a compound (5) and a compound (Ib) suitably with the target compound (14).

  More specifically, when both ends of the compound (14) are halogen atoms, the compound (5) is preferably used in excess. Specifically, the amount of compound (Ib) to be used is preferably 0.05 to 0.2 mol, more preferably 0.075 to 0.15 mol, per 1 mol of compound (5).

  Moreover, when making both ends of a compound (14) into boronic acid or its ester group, it is preferable to make compound (Ib) into excess amount. Specifically, the amount of compound (Ib) to be used is preferably 5 to 20 mol, more preferably 7 to 15 mol, per 1 mol of compound (5).

The above reaction is usually performed in the presence of a catalyst, and a palladium catalyst is preferably used. As this palladium-type catalyst, what was demonstrated by the method using the said Reaction formulas 1-3 is mentioned. In this step, Pd (PPh ₃ ) ₄ , Pd ₂ (dba) _{3 and the} like are preferable.

  In the case of using a palladium-based catalyst, the amount used is usually 0.001 to 1 mol with respect to 1 mol of the lesser compound of the starting compound (5) and compound (Ib) from the viewpoint of yield. Is preferable, and 0.005-0.5 mol is more preferable.

  Moreover, if necessary, a phosphorus ligand that can be coordinated to a palladium atom that is a central element of the palladium-based catalyst can be used together with the catalyst. As this phosphorus ligand, what was demonstrated by the method using the said Reaction formulas 1-3 is mentioned. In this step, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.

  When using a phosphorus ligand, the amount used is usually 0.01 to 1 mol of the compound (5) as the starting material and 1 mol of the smaller compound (Ib) from the viewpoint of yield. 1.0 mol is preferable, and 0.05 to 0.5 mol is more preferable.

  In addition to the palladium catalyst, a base (boron atom activator) may be used as necessary. Examples of this base include those described in the method using the above reaction formulas 1 to 3. Of these, cesium fluoride, cesium carbonate, silver carbonate, potassium phosphate and the like are preferable. The amount of the base used is usually preferably about 0.1 to 5.0 moles per mole of the starting compound (5) and the compound (Ib), which is the smaller of the compounds (Ib). More preferred is 0.0 mole.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include those described in the method using the above reaction formulas 1 to 3. Of these, cyclic ethers (such as tetrahydrofuran) are preferred in this step.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.

  The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

Compound (15)
The compound (15) is obtained by obtaining the compound (7a) according to the reaction formula (1) as described above, and further, the halogen atom at the terminal of the compound (7a) and the boronic acid at the terminal of the compound (Ib) or its ester group. It is obtained by reacting.

(Wherein R ¹ , R ² , X, Y, Y ′ and n are the same as above).

  It can also be obtained by reacting the terminal boronic acid or the ester group of compound (8) with the terminal halogen atom of compound (5).

(Wherein R ¹ , R ² , X, Y, Y ′ and n are the same as above).

  In this reaction, the compound (15) can be obtained as a C-shaped chain compound by utilizing the bent portion of the cyclohexane ring.

  It is preferable to use the Suzuki-Miyaura coupling reaction for the above reaction.

  Here, it is preferable to make compound (Ib) or compound (5) into an excess amount. Specifically, the amount of compound (Ib) to be used is preferably 5 to 20 mol, more preferably 7 to 15 mol, per 1 mol of compound (7a). Moreover, 5-20 mol is preferable with respect to 1 mol of compounds (8), and, as for the usage-amount of a compound (5), 7-15 mol is more preferable.

Here, a palladium-based catalyst is usually used. As this palladium-type catalyst, what was demonstrated by the method using the said Reaction formulas 1-3 is mentioned. Of these, Pd (PPh ₃ ) _{4 and the} like are preferable.

  From the viewpoint of yield, the amount of the palladium-based catalyst is usually preferably 0.001 to 1 mol, preferably 0.005 to 0.5 mol per mol of the raw material compound (7a) or compound (8). Mole is more preferred.

  Moreover, if necessary, a phosphorus ligand that can be coordinated to a palladium atom that is a central element of the palladium-based catalyst can be used. As this phosphorus ligand, what was demonstrated by the method using the said Reaction formulas 1-3 is mentioned. Of these, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.

  When the phosphorus ligand is used, the amount used is usually preferably 0.001 to 1.0 mol with respect to 1 mol of the starting compound (7a) or compound (8) from the viewpoint of yield. 0.01 to 0.8 mol is more preferable.

  In addition to the palladium catalyst, a base (boron atom activator) is preferably added. Examples of this base include those described in the method using the above reaction formulas 1 to 3. Preferred are sodium carbonate, silver carbonate and the like. The amount of the base (the activator) used is usually preferably from 0.01 to 10 mol, preferably from 0.1 to 5.0 mol, per 1 mol of the starting compound (7a) or compound (8). More preferred.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include those described in the method using the above reaction formulas 1 to 3. Of these, aromatic hydrocarbons (toluene and the like) are preferable in this step. Moreover, the system containing water may be sufficient.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.

  The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

Compound (16)
Compound (16) can be obtained, for example, by a reaction using compound (I) and compound (II). More specifically, it is obtained by reacting the terminal halogen atom of compound (5) or compound (10) with the terminal boronic acid of compound (6) or compound (Ib) or its ester group.

(Wherein R ¹ , R ² , R ⁴ , R ⁸ , X, Y, Y ′, n, m ′ and m1 are the same as above).

  In this reaction, compound (16) can be obtained as an L-shaped chain compound by utilizing the bent portion of the cyclohexane ring.

  It is preferable to use the Suzuki-Miyaura coupling reaction for the above reaction.

  Here, it is preferable to make compound (6) or compound (10) into an excessive amount. Specifically, the amount of compound (6) to be used is preferably 5 to 20 mol, more preferably 7 to 15 mol, per 1 mol of compound (5). Moreover, 5-20 mol is preferable with respect to 1 mol of compound (Ib), and, as for the usage-amount of a compound (10), 7-15 mol is more preferable.

Here, a palladium-based catalyst is usually used. As this palladium-type catalyst, what was demonstrated by the method using the said Reaction formulas 1-3 is mentioned. Of these, Pd (PPh ₃ ) _{4 and the} like are preferable.

  The amount of the palladium catalyst used is usually preferably from 0.0001 to 0.5 mol, preferably from 0.0005 to 0, per 1 mol of the starting compound (5) or compound (Ib) from the viewpoint of yield. More preferred is 2 moles.

  Moreover, if necessary, a phosphorus ligand that can be coordinated to a palladium atom that is a central element of the palladium-based catalyst can be used. As this phosphorus ligand, what was demonstrated by the method using the said Reaction formulas 1-3 is mentioned. Of these, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.

  When the above phosphorus ligand is used, the amount used is usually preferably 0.001 to 1.0 mol with respect to 1 mol of the starting compound (5) or compound (Ib) from the viewpoint of yield. 0.01 to 0.8 mol is more preferable.

  In addition to the palladium catalyst, a base (boron atom activator) is preferably added. Examples of this base include those described in the method using the above reaction formulas 1 to 3. Preferably, it is silver carbonate or the like. The amount of the base (the activator) used is usually preferably from 0.01 to 10 mol, preferably from 0.1 to 5.0 mol, based on 1 mol of the starting compound (5) or compound (Ib). More preferred.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include those described in the method using the above reaction formulas 1 to 3. Of these, in the present invention, cyclic ethers (such as tetrahydrofuran) are preferred.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.

  The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

<Method 1>
Cyclic compounds in which 9 to 13 (especially 9, 11 or 13) aromatic rings are linked are, for example,
General formula (III):
^X-R 9 -X
(In the formula, R ⁹ represents 3 to 4 general formulas (17):

(Wherein R ¹ is the same as defined above.)
And a divalent group comprising 6 or more (especially 6 to 9) phenylene groups or a divalent condensed polycyclic aromatic hydrocarbon group; X is the same as defined above. ]
And a step of obtaining a ring-shaped compound by reacting terminal atoms (particularly, halogen atoms) of the chain compound represented by formula (1) by an intramolecular ring-closing reaction.

  Here, a ring-shaped compound is obtained from the compound (III) by an intramolecular ring-closing reaction. In addition, compound (III) is obtained by making it react using the raw material demonstrated above.

  Compound (III) is a concept that includes compounds having both ends being a halogen atom among the compounds (14) and (15) among the compounds described above. Therefore, other compounds of compound (III) can also be obtained by the same method as the compound (14) and compound (15) in which both ends are halogen atoms.

  Here, the terminal atoms of the compound (III) are bonded to form a ring-shaped compound. Compound (III) has two halogen atoms. By using a nickel compound, the halogen atoms can be bonded to each other to cause an intramolecular ring-closing reaction.

  In this step, the number of rings that compound (III) has becomes the number of rings that the cyclic compound (especially carbon nanorings) has as it is. From this, it is possible to freely design the number of aromatic rings to be linked by suitably selecting the compound (III), and to efficiently produce a cyclic compound in which a desired number of aromatic rings are linked in a short process. Can be manufactured well.

  In the intramolecular ring closure reaction, a nickel compound is used. Examples of the nickel compound include those described in the method using the above reaction formula 3.

  The amount of the nickel compound used varies depending on the raw material used, but usually the amount of the nickel compound charged as a reagent is usually 0.01 to 50 mol, preferably 0, relative to 1 mol of the raw material compound (III). .1-10 moles.

  A ligand capable of coordinating to nickel (nickel atom) can be used together with the nickel compound. Examples of the ligand include those described in the method using the above reaction formula 3.

  When using the said ligand, the usage-amount is 0.01-50 mol normally with respect to 1 mol of compound (III), Preferably it is 0.1-10 mol.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include those described in the method using the above reaction formula 3. Of these, cyclic ethers (such as tetrahydrofuran) are preferred in this step.

  When using a reaction solvent, it is preferable to adjust the concentration of the raw material in various ways, but it is preferable not to make the concentration of the raw material too high. Specifically, the concentration of compound (III) is preferably 0.1 to 5 mmol / L, and more preferably 0.2 to 3 mol / L.

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.

  The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

  Thereby, a ring-shaped compound is obtained. When a compound in which both ends are halogen atoms is used as the raw material in the compound (14), the general formula (12b):

(Wherein R ¹ is the same as defined above.)
Is obtained.

Further, when a compound in which both ends of the compound (15) are halogen atoms, R ² is a 1,4-phenylene group and n is 1 is used as a raw material, the general formula (18):

(Wherein R ¹ is the same as defined above.)
Is obtained.

  In the same manner, the general formula (19):

(Wherein R ¹ is the same as defined above.)
And the like can also be obtained.

<Method 2>
A cyclic compound in which 10 to 13 (particularly 10) aromatic rings are linked is, for example,
Formula (IV-1):
Y'-R ^10a -Y '
(Wherein R ^10a represents three structural units represented by the general formula (17), 6 or more (especially 6 to 9) phenylene groups or divalent condensed polycyclic aromatic hydrocarbon groups; A divalent group comprising: Y ′ is the same as defined above.)
A compound represented by
General formula (IV-2):
Y′-R ^10b -Y ′
(In the formula, R ^10b is a divalent group consisting of one or more (particularly 1 to 4) phenylene groups or a divalent condensed polycyclic aromatic hydrocarbon group; Y ′ is the same as above).
Or a step of obtaining a ring-shaped compound by reacting with a compound represented by
Formula (V-1):
Y′-R ^11a -Y ′
[Wherein, R ^11a represents two structural units represented by the general formula (17), 4 or more (particularly 4 to 8) phenylene groups or divalent condensed polycyclic aromatic hydrocarbon groups, A divalent group consisting of: Y ′ is the same as defined above. ]
A compound represented by
General formula (V-2):
Y′-R ^11b -Y ′
[Wherein, R ^11b represents one structural unit represented by the general formula (17), two or more (particularly 2 to 6) phenylene groups, or a divalent condensed polycyclic aromatic hydrocarbon group, A divalent group consisting of: Y ′ is the same as defined above. ]
A step of obtaining a ring-shaped compound by reacting with a compound represented by the formula:

  That is, a ring-shaped compound is obtained by the reaction between the compound (IV-1) and the compound (IV-2) or the reaction between the compound (V-1) and the compound (V-2).

  Compound (IV-1) includes compound (14), and compound (IV-2) includes compound (II), compound (6), compound (10) and the like.

  From this, the reaction between the compound (IV-1) and the compound (IV-2), specifically, for example, the following reaction:

(Wherein R ¹ and Y ′ are the same as above).
Gives a ring-shaped compound.

  Compound (V-1) includes compound (8), and compound (V-2) includes compound (I), compound (Ib), compound (5), compound (16) and the like.

  From this, the reaction between the compound (V-1) and the compound (V-2), specifically, for example, the following reaction:

(Wherein R ¹ , R ² , X, Y and n are the same as above).
Gives a ring-shaped compound.

  In this way, even in a combination where it is considered that a ring-shaped compound having a roughly rectangular or substantially equilateral triangular shape cannot be synthesized by using the angle of the cyclohexane ring, a ring-shaped compound having a distorted shape cannot be obtained. it can. This makes it possible to synthesize cyclic compounds having various numbers of rings.

  Here, the reaction is not limited to the above reaction, and various combinations of compound (IV-1) and compound (IV-2), and combinations of compound (V-1) and compound (V-2) may be employed.

  It is preferable to use the Suzuki-Miyaura coupling reaction for the above reaction. That is, it is preferable that both ends of one of the compounds (IV-1) and (IV-2) are halogen atoms and both ends of the other compound are boronic acid or an ester group thereof. Further, it is preferable that both ends of one of the compounds (V-1) and (V-2) are halogen atoms and both ends of the other compound are boronic acid or an ester group thereof.

  0.01-5.0 mol is preferable with respect to 1 mol of compound (IV-1), and, as for the usage-amount of compound (IV-2), 0.05-3.0 mol is more preferable. Similarly, 0.01-5.0 mol is preferable with respect to 1 mol of compound (V-1), and, as for the usage-amount of compound (V-2), 0.05-3.0 mol is more preferable.

Here, a palladium-based catalyst is usually used. As this palladium-type catalyst, what was demonstrated by the method using the said Reaction formulas 1-3 is mentioned. Of these, Pd (OAc) ₂ (Ac is an acetyl group), bis (dibenzylideneacetone) palladium (0), bis (tri-t-butylphosphino) palladium (0), and the like are preferable.

  From the viewpoint of yield, the amount of the palladium-based catalyst is usually preferably from 0.0001 to 1.0 mol, based on 1 mol of the starting compound (IV-1) or compound (V-1). .0005 to 0.5 mol is more preferable.

  Moreover, if necessary, a phosphorus ligand that can be coordinated to a palladium atom that is a central element of the palladium-based catalyst can be used. As this phosphorus ligand, what was demonstrated by the method using the said Reaction formulas 1-3 is mentioned. Of these, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (X-Phos) and the like are preferable.

  When using the said phosphorus ligand, the usage-amount is 0.001-1. With respect to 1 mol of compounds (IV-1) or a compound (V-1) of a raw material from a viewpoint of a yield normally. 0 mol is preferable, and 0.01 to 0.8 mol is more preferable.

  In addition to the palladium catalyst, a base (boron atom activator) is preferably added. Examples of this base include those described in the method using the above reaction formulas 1 to 3. Preferred are sodium hydroxide and potassium phosphate. The amount of the base (the activator) used is usually preferably 0.01 to 10 moles per mole of the starting compound (IV-1) or compound (V-1), preferably 0.1 to 5 More preferred is 0.0 mole.

  The reaction is usually performed in the presence of a reaction solvent. Examples of the reaction solvent include those described in the method using the above reaction formulas 1 to 3. Among these, in this step, cyclic ethers (dioxane and the like) are preferable. Moreover, it is good also as a system containing water.

  When using a reaction solvent, it is preferable to adjust the concentration of the raw material in various ways, but it is preferable not to make the concentration of the raw material too high. For example, when reacting compound (14) and compound (II), the concentration of compound (14) is preferably from 0.1 to 5 mmol / L, more preferably from 0.2 to 3 mol / L. Similarly, when the compound (8) and the compound (5) are reacted, the concentration of the compound (8) is preferably 0.1 to 5 mmol / L, more preferably 0.2 to 3 mol / L. .

  The reaction temperature is usually selected from the range of 0 ° C. or higher and lower than the boiling temperature of the reaction solvent.

  The reaction atmosphere is not particularly limited, but is preferably an inert gas atmosphere, and may be an argon gas atmosphere, a nitrogen gas atmosphere, or the like. An air atmosphere can also be used.

  The ring-shaped compound thus obtained has 3 to 4 general formulas (17):

(Wherein R ¹ is the same as defined above.)
A structural unit represented by
6 to 9 phenylene groups or a divalent condensed polycyclic aromatic hydrocarbon group;
And
A cyclic compound having a total of 10, 11 or 13 structural units represented by the general formula (17) and a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group.

<Benzeneation of cyclohexane ring>
After obtaining a ring-shaped compound as described above, a cyclic compound is obtained by converting the cyclohexane ring portion into a benzene ring.

  The method can be carried out in the same manner as the method for converting the compound (11) in the above <Reaction formula 2> into the compound (3).

  In addition, if a cyclohexane ring part is converted into a benzene ring using a ring-shaped compound having 10, 11, or 13 rings, a cyclic compound in which 10, 11 or 13 aromatic rings are linked is obtained.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited at all by these Examples.

For thin layer chromatography (TLC), E. Merck silica gel 60 F254 precoated plates (0.25 mm thick) were used. The chromatogram was analyzed using a UV lamp (254 nm). Flash column chromatography (FCC) was performed using E. Merck silica gel 60 F254 (230-400 mesh). For preparative thin layer chromatography (PTLC), a Wakogel B5-F silica-coated plate (0.75 mm thick) was prepared and used. For recycle preparative gel permeation chromatography (GPC), JAI LC-9204 type (preparation column JAIGEL-1H / JAIGEL-2H, chloroform) was used. Mass spectra are Waters Micromass LCT Premier (electrospray ionization time-of-flight mass spectrometry, ESI-TOFMS), JEOL JMS700 (fast atom bombardment mass spectrometer, FAB-MS) Bruker Daltonics Ultraflex III TOF / TOF (MALDI-TOF-MS) ) Was used. Elemental analysis was performed using Yanako MT-6. Melting | fusing point was performed using MPA100 type | mold OptiMelt melting | fusing point measuring apparatus. Nuclear magnetic resonance (NMR) ^{spectra, JEOL GSX-270 (1 H} 270MHz, 13 C 67.5MHz) ^{spectrometer, JEOL JNM-ECS400 (1 H} 400MHz, 13 C 100MHz), JEOL JNM-ECA-600 (1 H 600MHz , ¹³ C 150 MHz) using a spectrometer in CDCl ₃ or DMSO-d6. Chemical shifts for ¹ H NMR were expressed in ppm relative to tetramethylsilane (δ0.00 ppm), CHCl ₃ (δ7.26 ppm), or CDCl ₂ (δ5.32 ppm). Chemical shifts for ¹³ C NMR were expressed in ppm relative to CDCl ₃ (δ 77.0 ppm).

Synthesis Example 1 Production of Compound (5a) In a 1 L round bottom flask having an internal volume of 1.68 g (33 mmol) of lithium chloride and 14.4 g (0.33 mol) of cerium (III) trichloride heptahydrate, The flask was immersed in an oil bath and dried by heating at 90 ° C. for 2 hours under vacuum. After the obtained reactant mixture was crushed into a powder, the powdered reactant mixture was put into the flask again. Further, the flask was immersed in an oil bath and heated at 90 ° C. for 1 hour under vacuum. A stir bar was placed in the flask, and the flask was again immersed in an oil bath and heated at 150 ° C. for 3 hours under vacuum while stirring. Before the contents in the flask were cooled, argon gas was charged into the flask. 200 mL of dry tetrahydrofuran (THF) was added and suspended therein, and the resulting suspension was stirred at room temperature (about 23 ° C., hereinafter the same) for about 8 hours. To this suspension, 15 mL of a THF solution of 1.68 g (15 mmol) of 1,4-cyclohexanedione was added using a cannula, stirred at room temperature for 2 hours, cooled to -78 ° C, and suspended. Liquid A was obtained.

In a 1 L round bottom flask different from the above, 10.7 g (45 mmol) of 1,4-dibromobenzene and 90 mL of dry THF were placed. Here, 29.5 mL (1.57 M, 45 mmol) of a hexane solution of n-butyllithium was gradually added dropwise at a temperature of -78 ° C. (addition rate: 4.5 cm ³ / min). After completion of dropping, the mixture was stirred at −78 ° C. for 30 minutes, and the obtained solution was put into the above suspension A using a cannula to obtain a mixture.

The mixture was stirred at −78 ° C. for 1 hour, and then stirred at room temperature for 2 hours. Then, 50 mL of saturated NH ₄ Cl aqueous solution was added to the mixture to stop the reaction. The product was filtered through celite, and the resulting filtrate was concentrated with an evaporator. Then, ethyl acetate was added to the resulting residue (concentrate) was extracted the crude product, and dried by anhydrous Na ₂ SO _4, to obtain an ethyl acetate solution. The solution was concentrated by an evaporator, and the residue (concentrate) was recrystallized from chloroform to obtain 5.32 g of a white solid substance. Then, by nuclear magnetic resonance analysis ^{(1 H NMR, 13 C NMR} ) and mass spectrometry, the results of analysis of this white solid material, the following formula (5a):

It was a compound shown by. The yield of this compound was 83%.

¹ H NMR (270 MHz, CDCl ₃ ) δ1.71 (s, 2H), d 2.07 (s, 8H), 7.34 (d, J = 8.6 Hz, 4H), 7.47 (d, J = 8.6 Hz, 4H) ; ¹³ C NMR (67.5 MHz, CDCl ₃ ) δ33.2 (CH ₂ ), 72.3 (4 °), 121.5 (4 °), 127.2 (CH), 131.6 (CH), 144.6 (4 °); HRMS (FAB , negative) m / z calcd for C ₁₈ H ₁₇ Br ₂ O ₂ [MH] ⁻ : 422.9595, found 422.9576; mp: 177.7-178.7 ℃.

Synthesis Example 2: Formation of MOM protection of hydroxyl group of compound (5a) In a 200 mL round bottom flask containing a stir bar, 4.69 g (11 mmol) of compound (5a) obtained in Synthesis Example 1 above and dry dichloromethane 44 mL of (CH ₂ Cl ₂ ) and 7.7 mL (44 mmol) of diisopropylethylamine were added, and the flask was immersed in an ice bath. And after stirring the mixture in a flask for 30 minutes at 0 degreeC, chloromethyl methyl ether 3.5 mL (46 mmol) was put. The mixture was then allowed to react with stirring at room temperature for 18 hours, after which 20 mL of saturated aqueous NH ₄ Cl was added to quench the reaction. The product was extracted with CH ₂ Cl ₂ (20 mL × 3), and the organic layer after extraction was dried over anhydrous Na ₂ SO ₄ to obtain a solution. The solution was concentrated by an evaporator, and the residue (concentrate) was purified by silica gel chromatography (CH ₂ Cl ₂ ) to obtain 5.48 g of a colorless solid substance. As a result of analyzing this colorless solid substance by nuclear magnetic resonance analysis ( ¹ H NMR, ¹³ C NMR) and mass spectrometry, the following formula (5b):

It was a compound shown by. The yield of this compound was 97%.

¹ H NMR (270 MHz, CDCl ₃ ) δ1.71 (s, 2H), 2.07 (s, 8H), 7.34 (d, J = 9 Hz, 4H), 7.47 (d, J = 9 Hz, 4H); 13C NMR (150 MHz, CDCl ₃ ) δ33.0 (CH ₂ ), 56.2 (CH ₃ ), 77.9 (4 °), 92.3 (CH ₂ ), 121.8 (4 °), 128.7 (CH), 131.6 (CH) , 141.6 (br, 4 °); HRMS (FAB) m / z calcd for C ₂₂ H ₂₆ Br ₂ O ₄ Na [M ⁺ Na] ⁺ : 535.0096, found 535.0103.mp: 107.1-108.9 ° C.

Synthesis Example 3: Production of Compound (6a) (1,4-Benzenediboronic acid neopentyl glycol ester) In a 50 mL round bottom flask containing a stirrer, p-phenylenebisboronic acid (125 mg, 0.75) was added. mmol, 1 equivalent), neopentyl glycol 250 mg (2.4 mmol, 3 equivalents), p-toluenesulfonic acid 50 mg and dry benzene (benzene) 10 mL. Thereafter, the mixture was reacted by refluxing at 70 ° C. for 12 hours. After cooling the mixture (reactant) in the flask to room temperature, the desired product was extracted with CH ₂ Cl ₂ . The organic layer after extraction was washed with a saturated aqueous NaHCO ₃ solution, and then the solvent was distilled off under reduced pressure to obtain 226.9 mg of the product. And as a result of analyzing this product by nuclear magnetic resonance analysis ( ¹ H NMR) and mass spectrometry, the following formula (6a):

It was a compound shown by. The yield of this compound was 99%.

¹ H NMR (270 MHz, CDCl ₃ ) δ 1.02 (s, 12H), 3.77 (s, 8H), 7.78 (s, 4H); LRMS (EI) m / z calcd for C ₁₆ H ₂₄ Br ₂ O ₄ [ M] ⁺ : 302.1861, found 302.

Synthesis Example 4: Production of Compound (6b) (4,4'-Biphenyldiboronic acid neopentyl glycol ester) Compound (6b):

Got. This compound is commercially available.

Synthesis Example 5: Production of compound (6c) having boronic acid or its ester group Into a 20 mL round bottom flask containing a stirring bar, 115.4 mg (0.40 mmol) of 2,6-dibromonaphthalene, bis (neopentylglycol) diboron Add 273.3 mg (1.2 mmol), (1,1'-bis (diphenylphosphino) ferrocene) dichloropalladium (II) 10.3 mg (13 μmol), and potassium acetate (KOAc) 244.8 mg (2.5 mmol). Filled into flask. Thereto, 2 mL of dry dimethyl sulfoxide was introduced to form a mixture, and the mixture was reacted at 80 ° C. for 21 hours while stirring. Subsequently, the mixture (reaction product) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered through silica gel. After the solvent was distilled off under reduced pressure from the obtained filtrate with an evaporator, the residue (concentrate) was recrystallized with hexane to obtain 47.8 mg of a white solid substance. Then, by nuclear magnetic resonance analysis ⁽¹ H NMR) and mass spectrometry, the results of analysis of this white solid material, the following equation (6c):

It was a compound shown by. The yield of this compound was 31%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 1.06 (s, 12H), 3.83 (s, 8H), 7.83 (s, 4H), 8.33 (s, 2H). LRMS (EI) m / z calcd for C ₂₀ H ₂₆ B ₂ O ₄ [M] ⁺ : 352, found 352.

Synthesis Example 6 Production of Compound (7a-1) (Part 1)
In a 200 mL round bottom flask containing a stir bar, 400 mg (2.6 mmol) of cesium fluoride, 2.07 g (4 mmol) of the compound (5b) obtained in Synthesis Example 2, and obtained in Synthesis Example 3 The compound (6a) 151.2 mg (0.5 mmol) and [Pd (PPh ₃ ) ₄ ] 30.1 mg (0.026 mmol) were added, and argon gas was charged into the flask. Thereto, 60 mL of dry THF was introduced to form a mixture, and this mixture was reacted at 65 ° C. for 26 hours while stirring. Next, the mixture (reaction solution) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered through celite. After the solvent was distilled off from the obtained filtrate under reduced pressure with an evaporator, the residue (concentrate) was purified by silica gel chromatography (hexane / EtOAc) to obtain 319.9 mg of a white solid substance. Then, by nuclear magnetic resonance analysis ^{(1 H NMR, 13 C NMR} ) and mass spectrometry, the results of analysis of this white solid material, the following formulas (7a-1):

It was a compound shown by. The yield of this compound was 68%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 2.11 (brs, 8H), 2.30-2.40 (brm, 8H), 3.42 (s, 6H), 3.43 (s, 6H), 4.44 (s, 4H), 4.48 ( s, 4H), 7.33 (d, J = 9 Hz, 4H), 7.45 (d, J = 9 Hz, 4H), 7.51 (d, J = 9 Hz, 4H), 7.60 (d, J = 9 Hz, 4H), 7.65 (s, 4H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 33.0 (CH ₂ ), 56.0 (CH ₃ ), 77.9 (4 ^o ), 78.1 (4 ^o ), 92.2 (CH ₂ ) , 92.3 (CH ₂ ), 121.7 (4 ^o ), 126.9 (CH), 127.4 (CH), 128.7 (4 ^o ), 131.5 (CH), 139.5 (4 ^o ), 139.8 (4 ^o ); HRMS (FAB) m / z calcd for C ₅₀ H ₅₆ Br ₂ O ₈ Na [M ⁺ Na] ⁺ : 965.2240, found 965.2195; mp: 184.7-186.4 ° C.

Synthesis Example 7: Production of Compound (7a-2) In a 50 mL round bottom flask containing a stirring bar, 165 mg (1.1 mmol) of cesium fluoride and 521.3 mg of Compound (5b) obtained in Synthesis Example 2 (1 mmol), the above compound (6b) 75.5 mg (0.2 mmol), and [Pd (PPh ₃ ) ₄ ] 6.8 mg (6 μmol) were added, and argon gas was charged into the flask. Thereto, 60 mL of dry THF was introduced to form a mixture, and this mixture was reacted at 65 ° C. for 26 hours while stirring. Subsequently, the mixture (reaction solution) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered through celite. After the obtained filtrate was evaporated under reduced pressure using an evaporator, the residue (concentrate) was purified by silica gel chromatography (hexane / EtOAc) to obtain 126.5 mg of a white solid substance. Then, by nuclear magnetic resonance analysis ^{(1 H NMR, 13 C NMR} ) and mass spectrometry, the results of analysis of this white solid material, the following formulas (7a-2):

It was a compound shown by. The yield of this compound was 62%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 2.11 (brs, 8H), 2.34−2.37 (brm, 8H), 3.41 (s, 6H), 3.43 (s, 6H), 4.44 (s, 4H), 4.48 ( s, 4H), 7.33 (d, J = 9 Hz, 4H), 7.45 (d, J = 9 Hz, 4H), 7.51 (d, J = 9 Hz, 4H), 7.60 (d, J = 9 Hz, 4H), 7.65 (s, 4H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 33.0 (CH ₂ ), 56.0 (CH ₃ ), 77.2 (4 °), 77.9 (4 °), 78.1 (4 °) , 92.2 (CH ₂ ), 92.3 (CH ₂ ), 121.7 (4 ^o ), 126.9 (CH), 127.4 (CH), 128.7 (4 °), 131.5 (CH), 139.5 (4 °), 139.8 (4 ° ); HRMS (FAB) m / z calcd for C ₅₆ H ₆₀ Br ₂ O ₈ Na [M ⁺ Na] ⁺ : 1041.2553, found 1041.2532.

Synthesis Example 8 Production of Compound (7a-3) (Part 1)
In a 50 mL round bottom flask containing a stir bar, cesium fluoride 80.2 mg (0.53 mmol), compound (5b) obtained in Synthesis Example 2, 349.7 mg (0.68 mmol), compound obtained in Synthesis Example 5 (6c) 32.0 mg (84 μmol) and [Pd (PPh ₃ ) ₄ ] 4.7 mg (4 μmol) were added, and argon gas was charged into the flask. Thereto, 60 mL of dry THF was introduced to form a mixture, and this mixture was reacted at 60 ° C. for 24 hours while stirring. Subsequently, the mixture (reaction solution) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered through celite. After the obtained filtrate was evaporated under reduced pressure using an evaporator, the residue (concentrate) was purified by silica gel chromatography (hexane / EtOAc) to obtain 66.1 mg of a white solid substance. Then, by nuclear magnetic resonance analysis ⁽¹ H NMR) and mass spectrometry, the results of analysis of this white solid material, the following formulas (7a-3):

It was a compound shown by. The yield of this compound was 79%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 2.13 (brs, 8H), 2.36 (brs, 8H), 3.42 (s, 6H), 3.44 (s, 6H), 4.44 (s, 4H), 4.50 (s, 4H), 7.33 (d, J = 8.3 Hz, 4H), 7.45 (d, J = 8.5 Hz, 4H), 7.54 (d, J = 8.3 Hz, 4H) 7.71 (d, J = 8.3 Hz, 4H), 7.74 (d, J = 8.6 Hz, 4H), 7.94 (d, J = 8.3 Hz, 2H), 8.03 (s, 2H) .LRMS (FAB) m / z calcd for C ₅₄ H ₅₈ Br ₂ O ₈ [M ] ⁺ : 994.2478, found 994.

Synthesis Example 9: Production of Compound (8a) (Borylation Reaction Product) In a 50 mL round bottom flask containing a stirrer, 285.4 mg of Compound (7a-1) obtained in Synthesis Example 6 or Synthesis Example 26 described below was added. (0.30 mmol), [Pd ₂ (dba) ₃ ] 6.0 mg (6.6 μmol), 2- (dicyclohexylphosphino-2 ′, 4 ′, 6′-tri-isopropyl-1,1′-biphenyl (hereinafter “ 13.3 mg (also referred to as “X-Phos”) (28 μmol), bispinacolate diboron 227.5 mg (0.9 mmol), and potassium acetate (KOAc) 180.1 mg (1.8 mmol) were charged, and argon gas was charged into the flask. To the mixture, 15 mL of dry dioxane (1,4-dioxane) was introduced to form a mixture, which was allowed to react for 5 hours at 90 ° C. with stirring, and the mixture (reaction solution) in the flask was cooled to room temperature. The mixture (reaction solution) was filtered through silica gel, and the resulting filtrate was evaporated under reduced pressure using an evaporator. , The residue (concentrate) was purified by gel permeation chromatography (chloroform) to give a white solid material 271.7 mg. The nuclear magnetic resonance analysis ^{(1 H NMR, 13 C NMR} ) and by mass spectrometry, the white solid As a result of analyzing the substance, the following formula (8a):

It was a compound shown by. The yield of this compound was 87%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 1.32 (s, 24H) 2.14 (brs, 8H), 2.36 (brs, 8H), 3.41 (s, 6H), 3.43 (s, 6H), 4.43 (s, 4H ), 4.48 (s, 4H), 7.46 (d, J = 8 Hz, 2H), 7.49 (d, J = 9 Hz, 2H), 7.45 (δ, J = 9 Hz, 4H), 7.51 (d, J = 8 Hz, 4H), 7.60 (d, J = 8.5 Hz, 4H), 7.65 (s, 4H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 24.9 (CH ₃ ), 33.0 (CH ₂ ), 56.0 (CH ₃ ), 78.2 (4 ^o ), 78.3 (4 ^o ), 83.8 (4 ^o ), 92.2 (CH ₂ ), 92.3 (CH ₂ ), 126.2 (4 ^o ), 126.9 (CH), 127.4 (CH) , 134.8 (4 ^o ), 134.9 (CH), 139.5 (4 ^o ), 139.7 (4 ^o ); HRMS (FAB) m / z calcd for C ₆₂ H ₈₀ B ₂ O ₁₂ Na [M ⁺ Na] ⁺ : 1061.5753 , found 1061.5719; mp: 225.1-226.6 ° C.

Synthesis Example 10 Production of Compound (8b) (Borylation Reaction Product) In a 50 mL round flask containing a stirring bar, 137 mg (134 μmol) of the compound (7a-2) obtained in Synthesis Example 7 [Pd ₂ (dba) ₃ ] 2.8 mg (3.1 μmol), bispinacolate diboron 106 mg (419 μmol), and potassium acetate (KOAc) 75.7 mg (771 μmol) were added, and argon gas was charged into the flask. Thereto, 5 mL of dry dioxane (1,4-dioxane) was introduced to prepare a mixture. The mixture was reacted at 90 ° C. for 5 hours with stirring. The mixture (reaction solution) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered through silica gel (EtOAc). After the obtained filtrate was evaporated under reduced pressure using an evaporator, the residue (concentrate) was purified by gel permeation chromatography to obtain 119 mg of a white solid substance. Then, by nuclear magnetic resonance analysis ^{(1 H NMR, 13 C NMR} ) and mass spectrometry, the results of analysis of this white solid material, the following formula (8b):

It was a compound shown by. The yield of this compound was 87%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 1.32 (s, 24H) 2.15 (brs, 8H), 2.37 (brs, 8H), 3.41 (s, 6H), 3.44 (s, 6H), 4.43 (s, 4H ), 4.49 (s, 4H), 7.47 (d, J = 8 Hz, 2H), 7.50 (d, J = 8 Hz, 2H), 7.60 (δ, J = 9 Hz, 4H), 7.70 (d, J = 9 Hz, 4H), 7.60 (d, J = 8.5 Hz, 4H), 7.78 (d, J = 8 Hz, 2H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ24.9 (CH ₃ ), 33.0 (CH ₂ ), 33.1 (CH ₂ ) 56.1 (CH ₃ ), 77.1 (4 ^o ), 78.3 (4 ^o ), 78.4 (4 ^o ), 83.9 (4 ^o ), 92.3 (CH ₂ ), 126.3 (CH) , 127.0 (CH), 127.4 (CH), 127.5 (CH), 134.9 (CH), 139.6 (4 ^o ), 139.7 (4 ^o ), 139.8 (4 ^o ); HRMS (FAB) m / z calcd for C ₅₆ H ₆₀ Br ₂ O ₈ Na [M ⁺ Na] ⁺ : 1041.2553, found 1041.2532.

Synthesis Example 11: Production of 14-ring organic compound (11a) In a 50 mL round bottom flask containing a stirrer, 19.7 mg (21 μmol) of compound (7a-1) obtained in Synthesis Example 6 was synthesized. Compound (8a) 29.1 mg (28 μmol), [Pd (OAc) ₂ ] 0.9 mg (4.0 μmol), and X-Phos 2.0 mg (4.2 μmol) obtained in 9 were placed, and argon gas was charged into the flask. did. 10 mL of dried 1,4-dioxane and 18 mL (0.18 mmol) of 10 M aqueous sodium hydroxide (NaOH) were introduced to form a mixture. The mixture was reacted at 80 ° C. for 24 hours with stirring. Thereafter, the mixture (reaction solution) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered through silica gel. After evaporating the solvent of the obtained filtrate with an evaporator under reduced pressure, the residue (concentrate) was purified by silica gel chromatography (CHCl ₃ / EtOAc = 1/1) to obtain a white solid substance (14.6 mg). Then, by nuclear magnetic resonance analysis ⁽¹ H NMR) and mass spectrometry, the results of analysis of this white solid material, the following formula (11a):

It was a ring-shaped compound formed by continuously bonding 14 phenylene groups and 14 cyclohexylene derivative groups. The yield of this ring-shaped compound was 45%.

¹ H NMR (600 MHz, CDCl ₃ ) δ 2.18 (brs, 16H), 2.39 (brs, 16H), 3.42 (s, 12H), 3.43 (s, 12H), 4.46 (s, 8H), 4.48 (s, 8H), 7.57 (m, 40H). LRMS (FAB) m / z calcd for C ₁₀₀ H ₁₁₂ O ₁₆ [M] ⁺ : 1569.7984, found 1570.

Synthesis Example 12: Production of carbon nanoring (3a) composed of cycloparaphenylene containing 14 benzene rings (part 1)
In a 2 mL glass vial containing a stir bar, 9.1 mg (5.0 μmol) of the ring-shaped compound (11a) obtained in Synthesis Example 11, 50 μL (5.0 μmol) of 0.1 M p-toluenesulfonic acid aqueous solution, and dry m -1 mL of xylene was added to make a mixture. This vial was placed in a microwave reactor (Initiator Synthesis System, manufactured by Biotage), and reacted at 150 ° C. for 30 minutes while stirring. Next, the mixture (reaction solution) in the vial was cooled to room temperature, and the mixture (reaction solution) was filtered through silica gel. The obtained filtrate was evaporated under reduced pressure using an evaporator, and the residue (concentrate) was purified by silica gel chromatography (CH ₂ Cl ₂ / hexane) to obtain a white solid substance (1.1 mg). Then, by nuclear magnetic resonance analysis ⁽¹ H NMR) and mass spectrometry, the results of analysis of this white solid material, the following formula (3a):

It was [14] cycloparaphenylene (amorphous) which consists of 14 benzene rings shown by these. The yield of [14] cycloparaphenylene was 20%.

¹ H NMR (600 MHz CDCl ₃ ) δ7.65 (s, 56H). MS (MALDI-TOF) m / z calcd for C ₈₄ H ₅₆ [M] ⁺ : 1064.4382, found 1064.424.

Synthesis Example 13: Production of carbon nanoring (3a) composed of cycloparaphenylene containing 14 benzene rings (part 2)
In a 20 mL Schlenk tube containing a stir bar, 7.9 mg (5.0 μmol) of the annular compound (11a) obtained in Synthesis Example 11, 15.4 mg (11.3 μmol) of sodium hydrogensulfate monohydrate, dry m-xylene 1 mL and 1 mL of dried dimethyl sulfoxide (DMSO) were added to prepare a mixture. The mixture was reacted at 150 ° C. for 48 hours with stirring. Next, the mixture (reaction solution) in the Schlenk tube was cooled to room temperature, and the mixture (reaction solution) was extracted with CHCl ₃ . The organic layer after extraction was dried over Na ₂ SO ₄ and then the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel preparative thin layer chromatography (CH ₂ Cl ₂ / hexane) to give a white solid material (2.0 mg). Then, as a result of analyzing this white solid substance by nuclear magnetic resonance analysis ( ¹ H NMR, ¹³ C NMR) and mass spectrometry), [14] cycloparaffin consisting of 14 benzene rings represented by the above formula (3a) is shown. It was phenylene (amorphous). The yield of [14] cycloparaphenylene was 37%.

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.65 (s, 56H); ¹³ C NMR (98.5 MHz, CDCl ₃ ) δ 127.4 (CH), 138.8 (4 ^o ); HRMS (MALDI-TOF) m / z calcd for C ₈₄ H ₅₆ [M] ⁺ : 1064.4382, found 1064.438.

Synthesis Example 14: Production of 15 organic ring-shaped compound (11b) In a 50 mL round bottom flask containing a stirring bar, 20.0 mg (20 μmol) of the compound (7a-2) obtained in Synthesis Example 7 was synthesized. Compound (8a) 285.4 mg (29 μmol), [Pd (OAc) ₂ ] 1.0 mg (4.4 μmol), and X-Phos 2.2 mg (4.6 μmol) were added, and argon gas was charged into the flask. . 20 mL of dry 1,4-dioxane and 19 mL (0.19 mmol) of 10 M NaOH aqueous solution were introduced to form a mixture. The mixture was reacted at 80 ° C. for 24 hours with stirring. Thereafter, the mixture (reaction solution) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered through silica gel. After the solvent was distilled off under reduced pressure with the evaporator of the obtained filtrate, the residue (concentrate) was purified by silica gel chromatography (CHCl ₃ / EtOAc = 1/1) to obtain a white solid substance (10.4 mg). Then, by nuclear magnetic resonance analysis ⁽¹ H NMR) and mass spectrometry, the results of analysis of this white solid material, the following formula (11b):

It was a ring-shaped compound formed by continuously bonding 15 phenylene groups and cyclohexylene derivative groups. The yield of this cyclic compound was 32%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 2.18 (brs, 16H), 2.39 (brs, 16H), 3.44 (m, 24H), 4.48 (m, 16H), 7.57 (m, 44H). HRMS (FAB) m / z calcd for C ₁₀₆ H ₁₁₆ O ₁₆ [M] ⁺ : 1645.8297, found 1646.

Synthesis Example 15: Production of carbon nanoring (3b) composed of cycloparaphenylene containing 15 benzene rings (part 1)
In a 2 mL glass vial containing a stir bar, 9.8 mg (6.0 μmol) of the ring-shaped compound (11b) obtained in Synthesis Example 14, 120 μL (12 μmol) of 0.1 M p-toluenesulfonic acid aqueous solution, and dry m-xylene 1 mL was added to make a mixture. The vial containing the mixture was placed in a microwave reactor in the same manner as in Synthesis Example 12, and reacted at 150 ° C. for 30 minutes while stirring. Next, the mixture (reaction solution) in the vial was cooled to room temperature, and the mixture (reaction solution) was filtered through silica gel. The solvent of the obtained filtrate was distilled off under reduced pressure using an evaporator, and then the residue (concentrate) was purified by silica gel chromatography (CH ₂ Cl ₂ / hexane) to obtain a white solid substance (0.5 mg). Then, by nuclear magnetic resonance analysis ⁽¹ H NMR) and mass spectrometry, the results of analysis of this white solid material, the following formula (3b):

[15] cycloparaphenylene (amorphous) consisting of 15 benzene rings. The yield of [15] cycloparaphenylene was 7%.

¹ H NMR (400 MHz CDCl ₃ ) δ 7.67 (s, 60H). MS (MALDI-TOF) m / z calcd for C ₉₀ H ₆₀ [M] ⁺ : 1140.4695, found 1140.513.

Synthesis Example 16: Production of carbon nanoring (3b) composed of cycloparaphenylene containing 15 benzene rings (part 2)
In a 20 mL Schlenk tube containing a stir bar, 7.4 mg (4.5 μmol) of the ring-shaped compound (11b) obtained in Synthesis Example 14, 14.7 mg (10.6 μmol) of sodium hydrogen sulfate monohydrate, dry m-xylene 1 mL and 1 mL of dry dimethyl sulfoxide (DMSO) were added to prepare a mixture. The mixture was reacted at 150 ° C. for 48 hours with stirring. Next, the mixture (reaction solution) in the Schlenk tube was cooled to room temperature, and the mixture (reaction solution) was extracted with CHCl ₃ . The organic layer after extraction was dried over Na ₂ SO ₄ and then the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel preparative thin layer chromatography (CH ₂ Cl ₂ / hexane) to give a white solid material (2.2 mg). Then, as a result of analyzing this white solid substance by nuclear magnetic resonance analysis ( ¹ H NMR, ¹³ C NMR) and mass spectrometry, [15] cycloparaphenylene consisting of 15 benzene rings represented by the above formula (3b). (Amorphous). The yield of [15] cycloparaphenylene was 43%.

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.67 (s, 60H); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 127.3 (CH), 138.8 (4 ^o ); HRMS (MALDI-TOF) m / z calcd for C ₉₀ H ₆₀ [M] ⁺ : 1140.4695, found 1140.469.

Synthesis Example 17: Production of Ring Compound (11c) with 16 Organic Rings In a 50 mL round flask containing a stir bar, 42.8 mg (38.0 μmol) of Compound (7a-2) obtained in Synthesis Example 7 was synthesized. Compound (8b) 26.7 mg (26.2 μmol) [Pd (OAc) ₂ ] 1.3 mg (5.7 μmol) obtained in 10 and X-Phos 6.9 mg (14.4 μmol) were charged, and argon gas was charged into the flask. did. After introducing 13.5 mL of dry 1,4-dioxane and 27.0 μL (270 μmol) of 10 M NaOH aqueous solution to make a mixture, the mixture was reacted at 80 ° C. for 24 hours while stirring. Thereafter, the mixture (reaction solution) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered through silica gel (EtOAc). After the obtained filtrate was evaporated under reduced pressure using an evaporator, the residue (concentrate) was purified by silica gel preparative thin layer chromatography (CHCl ₃ : EtOAc = 1: 1) to obtain a white solid substance (15.5 mg). Then, by nuclear magnetic resonance analysis ^{(1 H NMR, 13 C NMR} ) and mass spectrometry, the results of analysis of this white solid material, the following formula (11c):

It was a ring-shaped compound formed by continuously bonding 16 phenylene groups and 16 cyclohexylene derivative groups. The yield of this cyclic compound was 32%.

¹ H NMR (270 MHz, CDCl ₃ ) δ 2.19 (brs, 16H), 2.40 (brs, 16H), 3.43 (s, 12H), 3.45 (s, 12H), 4.48 (s, 8H), 4.50 (s, 8H), 7.50-7.70 (m, 48H); ¹³ C NMR (98.5 MHz, CDCl ₃ ) δ 33.1 (CH ₂ ), 56.1 (CH ₃ ), 78.2 (4 ^o ), 92.3 (CH ₂ ), 126.9 (CH ), 127.4 (CH), 127.5 (CH), 139.6 (CH), 139.8 (4 ^o ); HRMS (FAB) m / z calcd for C ₁₁₂ H ₁₂₀ O ₁₆ Na [M ⁺ Na] ⁺ : 1743.8474, found 1743.8496 .

Synthesis Example 18: Production of carbon nanoring (3c) composed of cycloparaphenylene containing 16 benzene rings A 20 mL Schlenk tube containing a stirrer was charged with 12.5 mg (7.26) of the cyclic compound (11c) obtained in Synthesis Example 17. μmol), 20.0 mg (145 μmol) of sodium hydrogensulfate monohydrate, 1.2 mL of dry m-xylene, and 1.2 mL of dry dimethyl sulfoxide (DMSO) were added to form a mixture. The mixture was reacted at 160 ° C. for 48 hours with stirring. Next, the mixture (reaction solution) in the Schlenk tube was cooled to room temperature, and the mixture (reaction solution) was extracted with CHCl ₃ . The organic layer after extraction was dried over Na ₂ SO ₄ and then the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel preparative thin layer chromatography (CH ₂ Cl ₂ / hexane) to give a white solid material (2.5 mg). Then, by nuclear magnetic resonance analysis ^{(1 H NMR, 13 C NMR} ) and mass spectrometry, the results of analysis of this white solid material, the following formula (3c):

It was [16] cycloparaphenylene (amorphous) consisting of 16 benzene rings. The yield of [16] cycloparaphenylene was 28%.

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.68 (s, 64H); ¹³ C NMR (98.5 MHz, CDCl ₃ ) δ 127.3 (CH), 138.9 (4 ^o ); HRMS (MALDI-TOF) m / z calcd for C ₉₆ H ₆₄ [M] ⁺ : 1216.5008, found 121.

Synthesis Example 19 Production of Ring Compound (11d) with 14 Organic Rings Containing Naphthylene Ring (Part 1)
In a 50 mL round bottom flask containing a stir bar, 20.0 mg (20 μmol) of the compound (7a-3) obtained in Synthesis Example 8, 29.4 mg (28 μmol) of the compound (8a) obtained in Synthesis Example 9, [Pd (OAc) ₂ ] 0.9 mg (4.0 μmol) and X-Phos 2.0 mg (4.2 μmol) were added, and argon gas was charged into the flask. After introducing 10 mL of dry 1,4-dioxane and 10 μL (0.10 mmol) of 10 M sodium hydroxide (NaOH) aqueous solution to make a mixture, the mixture was reacted at 80 ° C. for 24 hours while stirring. Thereafter, the mixture (reaction solution) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered through silica gel. After the solvent was distilled off under reduced pressure with the evaporator of the obtained filtrate, the residue (concentrate) was purified by silica gel chromatography (CHCl ₃ / EtOAc = 1/1) to obtain a white solid substance (4.0 mg). Then, by nuclear magnetic resonance analysis ⁽¹ H NMR) and mass spectrometry, the results of analysis of this white solid material, the following formula (11d):

It was a cyclic compound in which 14 organic rings containing a phenylene group, a naphthylene group, and a cyclohexylene group derivative were continuously bonded. The yield of this cyclic compound was 12%.

¹ H NMR (270 MHz, CDCl ₃ ) δ 2.14 (brs, 16H), 2.38 (brs, 16H), 3.43 (m, 24H), 4.48 (m, 16H), 7.60 (m, 38H), 7.91 (d, J = 8.6 Hz, 2H), 8.01 (s, 2H). LRMS (FAB) m / z calcd for C ₁₀₄ H ₁₁₄ O ₁₆ [M] ⁺ : 1619.8140, found 1620.

Synthesis Example 20 Production of Compound (7a-3) (Part 2)
In a 100 mL round bottom flask containing a stirrer, 2.49 g (4.84 mmol) of the compound (5b) obtained in Synthesis Example 2, 190 mg (500 μmol) of the compound (6c) obtained in Synthesis Example 5 and Pd ( PPh ₃ ) ₄ 15.0 mg (13.0 μmol), sodium carbonate (Na ₂ CO ₃ ) 268 mg (2.53 mmol), tetra n-butylammonium bromide (n-Bu ₄ NBr) 555 mg (499 μmol), dried 20 mL of THF and 5 mL of water bubbled with argon gas were added. The mixture was reacted at 60 ° C. for 24 hours with stirring. Subsequently, the mixture (reaction solution) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered under reduced pressure. The residue (concentrate) was extracted with EtOAc, dried over Na ₂ SO ₄ and filtered under reduced pressure. The crude product was purified by silica gel chromatography (hexane / EtOAc = 8: 1 to 2: 1) to obtain 359 mg of a white solid substance. Then, by nuclear magnetic resonance analysis ⁽¹ H NMR and ¹³ C NMR) and mass spectrometry, the results of analysis of this white solid material, the following formulas (7a-3):

It was a compound shown by. The yield of this compound was 72%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 2.12 (brs, 8H), 2.27-2.48 (brm, 8H), 3.42 (s, 6H), 3.44 (s, 6H), 4.44 (s, 4H), 4.50 ( s, 4H), 7.33 (d, J = 8 Hz, 4H), 7.45 (d, J = 8 Hz, 4H), 7.55 (d, J = 8 Hz, 4H), 7.70 (d, J = 8 Hz, 4H), 7.75 (dd, J = 8 Hz, 1 Hz, 4H), 7.94 (d, J = 8 Hz, 2H), 8.04 (d, J = 1 Hz, 2H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 33.0 (CH ₂ ), 56.1 (CH ₃ ), 77.2 (4 °), 77.9 (4 °), 78.1 (4 °), 92.2 (CH ₂ ), 92.3 (CH ₂ ), 121.7 (4 °) , 126.9 (CH), 127.4 (CH), 128.7 (4 °), 131.5 (CH), 139.5 (4 °), 139.8 (4 °); HRMS (FAB) m / z calcd for C ₅₄ H ₅₈ Br ₂ O ₈ Na [M ⁺ Na] ⁺ : 1015.2396, found 1015.2394; mp: 193.6-194.4 ℃.

Synthesis Example 21 Production of Ring Compound (11d) with 14 Organic Rings Containing Naphthylene Ring (Part 2)
In a 50 mL Schlenk tube containing a stirrer, 40.1 mg (40.3 μmol) of the compound (7a-3) obtained in Synthesis Example 20 and 50.2 mg (48.3 μmol) of the compound (8a) obtained in Synthesis Example 9 were obtained. Then, 3.6 mg (3.9 μmol) of Pd ₂ (dba) ₃ , 3.7 mg (7.8 μmol) of X-Phos, and 85.0 mg (400 μmol) of K ₃ PO ₄ were added. The flask was then evacuated and filled with argon gas three times. To this flask, 20 mL of 1,4-dioxane bubbled with argon gas and 80 μL of water bubbled with argon were added under an argon stream. After stirring at 80 ° C. for 24 hours, the solvent was removed by passing through a silica gel layer (EtOAc). Thereafter, the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by gel permeation chromatography and preparative thin layer chromatography (CHCl ₃ / EtOAc = 1: 1) to give 22.6 mg of white solid material. Then, by nuclear magnetic resonance analysis ⁽¹ H NMR and ¹³ C NMR) and mass spectrometry, the results of analysis of this white solid material, the following formula (11d):

It was a ring-shaped compound shown by. The yield of this cyclic compound was 35%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 1.80-2.66 (brm, 32H), 3.42 (s, 6H), 3.44 (s, 18H), 4.45 (s, 4H), 4.46 (s, 4H), 4.49 ( s, 4H), 4.53 (s, 4H), 7.40-7.66 (m, 32H), 7.69 (d, J = 8 Hz, 4H), 7.73 (d, J = 9 Hz, 2H), 7.92 (d, J = 9 Hz, 2H), 8.02 (s, 2H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 33.0 (CH ₂ ), 55.9 (CH ₃ ), 56.1 (CH ₃ ), 77.94 (4 °), 78.00 (4 °), 78.1 (4 °), 78.2 (4 °), 92.1 (CH ₂ ), 92.2 (CH ₂ ), 125.4 (CH), 125.8 (CH), 126.8 (CH), 127.2 (CH), 127.3 (CH), 128.3 (CH), 128.7 (CH), 137.9 (4 °), 139.4 (4 °) 139.5 (4 °), 139.6 (4 °) 139.7 (4 °), 140.1 (4 °) 141.6 (br HRMS (FAB) m / z calcd for C ₁₀₄ H ₁₁₄ O ₁₆ Na [M ⁺ Na] ⁺ : 1641.8005, found 1641.8009; mp: 235.0-240.0 ° C (dec.).

Synthesis Example 22: Production of carbon nanoring (3d) consisting of 14 organic rings containing a naphthylene ring Into a 20 mL Schlenk tube containing a stirrer and a condenser, a ring compound (11d) obtained in Synthesis Example 19 or 21 16.2 mg (10.0 μmol), sodium hydrogen sulfate monohydrate (NaHSO ₄ · H ₂ O) 27.2 mg (197 μmol), dry DMSO 1 mL and m-xylene 2.0 mL were added. The mixture was heated at 150 ° C. for 24 hours with stirring under an air atmosphere. The mixture was cooled to room temperature and the solvent was removed by passing through a silica gel layer (CHCl ₃ ). Thereafter, the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by thin layer chromatography (CH ₂ Cl ₂ / hexane) to obtain a pale yellow solid material (2.8 mg). Then, by nuclear magnetic resonance analysis ⁽¹ H NMR and ¹³ C NMR) and mass spectrometry, the results of analysis of this light yellow solid substance, the following formula (3d):

It was a carbon nanoring consisting of 14 organic rings including a naphthylene ring. The yield of this carbon nanoring was 25%.

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.657 (brs, 44H), 7.670 (d, J = 8 Hz, 4H), 7.74 (d, J = 8 Hz, 4H), 7.77 (d, J = 9 Hz , 2H), 7.87 (d, J = 9 Hz, 2H), 8.01 (s, 2H); ¹³ C NMR (150 MHz, CDCl3) δ 125.5 (CH), 125.7 (CH), 127.3 (CH), 127.4 ( CH), 127.5 (CH), 127.6 (CH), 128.7 (CH), 133.1 (4 °), 137.3 (4 °), 138.7 (4 °), 138.78 (4 °), 138.82 (4 °), 138.84 ( 4 °), 138.9 (4 °), 139.1 (4 °); HRMS (MALDI-TOF) m / z calcd for C ₈₄ H ₅₆ [M] ⁺ : 1114.4543, found 1114.4539.

Synthesis Example 23: Production of [9] cycloparaphenylene and [12] cycloparaphenylene (1) Production of annular compounds (12a) and (12b-1)
In a glass round bottom flask equipped with a 200 mL stirrer, bis (1,5-cyclooctadiene) nickel (zero valent) 452 mg (1.64 mmol), 423 mg (823 μmol) of the compound (5b) obtained in Synthesis Example 2 was obtained. ), 2,2′-bipyridyl 257 mg (1.65 mmol). Here, 166 mL of THF was added by a syringe. The mixture was then stirred under reflux for 24 hours. After cooling to room temperature, the mixture was passed through a silica gel layer and washed with a mixed solvent of EtOAc / CHCl ₃ . Thereafter, the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (hexane / EtOAc), and the following formula (12a):

A cyclized tetramer (68.1 mg) represented by the following formula (12b-1):

The cyclized trimer represented by (95.5 mg) was obtained. Yields were 23% for cyclized tetramer and 32% for cyclized trimer, respectively. These materials were analyzed by ¹ H NMR and ¹³ C NMR.

Cyclized tetramer (12a):
¹ H NMR (400 MHz CDCl ₃ ) δ 2.16 (brs, 16H), 2.37 (brs, 16H), 3.42 (s, 16H), 4.45 (s, 16H), 7.50 (s, 32H).
Cyclized trimer (12b-1):
¹ H NMR (600 MHz, 50 ° C, CDCl ₃ ) δ 2.07 (brs, 12H), 2.28-2.34 (m, 12H), 3.43 (s, 18H), 4.58 (s, 12H), 7.40 (d, J = 8 Hz, 12H), 7.46 (d, J = 8 Hz, 12H); ¹³ C NMR (150 MHz, 50 ° C, CDCl ₃ ) δ 33.3 (CH ₂ ), 55.9 (CH ₃ ), 78.1 (4 °), 92.4 (CH ₂ ), 126.8 (CH), 127.3 (CH), 139.4 (4 °), 141.2 (4 °); HRMS (FAB) m / z calcd for C ₆₆ H ₇₈ NaO ₁₂ [M ・ Na] ⁺ : 1085.5391, found: 1085.538; mp: 182.3-187.0 ° C.

(2) Production of [9] cycloparaphenylene (4b)
In a Schlenk tube with a 20 mL stirrer and a condenser, the cyclized trimer represented by the above formula (12b-1) or 26.6 mg (25 μmol) of the compound (12b-1) obtained in Synthesis Example 30 described later Sodium hydrogen sulfate monohydrate 69.1 mg (400 μmol), dry dimethyl sulfoxide 1.5 mL and dry m-xylene 5 mL were accommodated and heated at 150 ° C. for 48 hours with stirring. After cooling to room temperature, the mixture (reaction solution) was extracted with CHCl ₃ . After extraction and drying with Na ₂ SO ₄ , the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, 4.2 mg of a yellow solid was isolated by TLC (CH ₂ Cl ₂ / hexane). And as a result of analyzing this substance by ¹ H NMR and ¹³ C NMR, the following formula (4b):

[9] cycloparaphenylene (amorphous) consisting of 9 p-phenylene groups. The yield was 24%.

  [9] Cycloparaphenylene (amorphous) and THF were placed in a reaction vessel to obtain a saturated solution. Next, the reaction vessel was opened and left standing in a vapor of pentane (10 ° C., 24 hours) to obtain [9] cycloparaphenylene crystals. From the X-ray structure analysis of the crystal, THF was included in the ring of [9] cycloparaphenylene crystal. [9] Cycloparaphenylene crystals are arranged regularly while adjoining each other while maintaining an angle of 5 to 45 degrees. Was forming.

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.52 (s, 36H); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 127.3 (CH), 137.9 (4 °); HRMS (MALDI-TOF) m / z calcd for C ₅₄ H ₃₆ [M ・] ⁺ : 684.2817, found: 684.2834.

(3) Production of [12] cycloparaphenylene (4a) The compound (12a) obtained in the above (1) is treated in the same manner as in the above (2) to obtain the following formula (4a):

[12] cycloparaphenylene ([12] CPP) consisting of 12 p-phenylene groups was obtained.

¹ H NMR (400 MHz CDCl ₃ ) δ 7.61 (s, 48H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ 127.33, 138.52.

Synthesis Example 24 Production of Compound (Ib-1)

In a 50 ml Schlenk tube containing a stirrer, 518 mg (1.0 mmol) of the compound (5b) obtained in Synthesis Example 2 above, 636 mg (2.5 mmol) of bis (pinacolate) diboron, 1,1'-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane complex (PdCl ₂ (dppf) · CH ₂ Cl ₂ ) 23.2 mg (30 μmol), potassium acetate (KOAc) 624 mg (6.35 mmol) , And 20 mL of dry dimethyl sulfoxide (DMSO). The Schlenk tube was heated at 80 ° C. for 17 hours with stirring. The reaction mixture was cooled to room temperature and then quenched with water. The product was extracted with ethyl acetate (EtOAc) and the organic phase was dried over Na ₂ SO ₄ and concentrated under reduced pressure. The crude product was purified by recycle preparative gel permeation chromatography (chloroform) to obtain 390 mg of the target compound as a white solid (yield 64%).

¹ H NMR (600 MHz, CDCl ₃ ) δ1.33 (s, 24H), 2.09 (br, 4H), 2.31 (br, 4H), 3.40 (s, 6H), 4.41 (s, 4H), 7.43 (d , J = 8 Hz, 4H), 7.76 (d, J = 8 Hz, 4H); ¹³ C NMR (150 MHz, CDCl ₃ ) δ24.9 (CH ₃ ), 32.9 (CH ₂ ), 56.0 (CH ₃ ) , 78.3 (4 °), 83.8 (4 °), 92.2 (CH ₂ ), 126.2 (CH), 128.1 (4 °), 134.8 (CH); HRMS (FAB) m / z calcd for C ₃₄ H ₅₀ B ₂ NaO ₈ [M ・ Na] ⁺ : 631.3584, found 631.3605.

It should be noted that the same conditions (however, 2.7 mmol of bis (pinacolato) diboron and 32 μmol of PdCl ₂ (dppf) · CH ₂ Cl ₂ ) were used instead of the compound (5b) at both ends instead of the compound at both ends bromine atom. , KOAc was adjusted to 9.0 mmol), and the yield could be improved to 83%.

Synthesis Example 25 Production of Compound (14-1)

In a 200 ml round bottom glass flask containing a stir bar, 5.58 g (10.9 mmol) of the compound (5b) obtained in Synthesis Example 2 above, 608 mg of the compound (Ib-1) obtained in Synthesis Example 24 above. (1.00 mmol), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 114 mg (98.2 μmol), silver carbonate (Ag ₂ CO ₃ ) 983 mg (3.57 mmol) and dry THF 100 mL It was. The resulting mixture was reacted under reflux for 38 hours with stirring. The reaction mixture was cooled to room temperature and then quenched with water. The product was extracted with ethyl acetate (EtOAc) and the organic phase was dried over Na ₂ SO ₄ and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (hexane / EtOAc = 5/1 to 1/1) to obtain 789 mg of the target compound as a colorless solid (yield 65%).

¹ H NMR (600 MHz, CDCl ₃ ) δ2.11 (brs, 12H), 2.28-2.43 (m, 12H), 3.40 (s, 6H), 3.42 (s, 6H), 3.43 (s, 6H), 4.43 (s, 4H), 4.46 (s, 4H), 4.48 (s, 4H), 7.31 (d, J = 8 Hz, 4H), 7.43 (d, J = 8 Hz, 4H), 7.47-7.57 (m, 16H); ¹³ C NMR (150 MHz, CDCl ₃ ) δ32.8 (CH ₂ ), 55.9 (CH ₃ ), 77.8 (4 °), 77.9 (4 °), 78.0 (4 °), 92.0 (CH ₂ ) , 92.1 (CH ₂ ), 121.5 (4 °), 126.8 (CH), 126.8 (CH), 127.2 (CH), 128.6 (CH), 131.4 (CH), 139.4 (4 °), 139.5 (4 °), 141.5 (br, 4 °); HRMS (FAB) m / z calcd for C ₆₆ H ₇₈ Br ₂ NaO ₁₂ [M ・ Na] ⁺ : 1243.3752, found: 1243.3760.

  The reaction was conducted at 60 ° C. for 24 hours, and the others were carried out in the same manner. The yield was 59%.

Synthesis Example 26 Production of Compound (7a-1) (Part 2)

In a 200 ml round bottom flask containing a stir bar, 400 mg (2.6 mmol) of cesium fluoride, 2.07 g (4 mmol) of compound (5b) obtained in Synthesis Example 2, and compound (6d) (1 , 4-Benzenediboronic acid bis (pinacol) ester, 1,4-benzenediboronic acid bis (pinacol) ester) 151.2 mg (0.5 mmol), and tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 30.1 mg (0.026 mmol) was charged, and argon gas was charged into the flask. Thereto, 60 ml of dry THF was introduced to form a mixture, and this mixture was reacted at 65 ° C. for 26 hours while stirring. Next, the mixture (reaction solution) in the flask was cooled to room temperature, and the mixture (reaction solution) was filtered through celite. After evaporating the solvent from the obtained filtrate under reduced pressure with an evaporator, the residue (concentrate) was purified by silica gel chromatography (hexane / EtOAc) to obtain 319.9 mg of the target compound as a white solid (yield 68%).

¹ H NMR (400 MHz, CDCl ₃ ) δ2.11 (brs, 8H), 2.30-2.40 (brm, 8H), 3.42 (s, 6H), 3.43 (s, 6H), 4.44 (s, 4H), 4.48 (s, 4H), 7.33 (d, J = 9 Hz, 4H), 7.45 (d, J = 9 Hz, 4H), 7.51 (d, J = 9 Hz, 4H), 7.60 (d, J = 9 Hz , 4H), 7.65 (s, 4H); ¹³ C NMR (100 MHz, CDCl ₃ ) δ33.0 (CH ₂ ), 56.0 (CH ₃ ), 77.9 (4 °), 78.1 (4 °), 92.2 (CH ₂ ), 92.3 (CH ₂ ), 121.7 (4 °), 126.9 (CH), 127.4 (CH), 128.7 (4 °), 131.5 (CH), 139.5 (4 °), 139.8 (4 °); HRMS ( FAB) m / z calcd for C ₅₀ H ₅₆ Br ₂ O ₈ Na [M ⁺ Na] ⁺ : 965.2240, found 965.2195; mp: 184.7-186.4 ° C.

Synthesis Example 27: Production of compound (16a)

In a 100 ml flask containing a stir bar, 366 mg (712 μmol) of the compound (5b) obtained in Synthesis Example 2, compound (6d) (1,4-benzenediboronic acid bis (pinacol) ester, 1,4- benzenediboronic acid bis (pinacol) ester) 1.99 g (6.03 mmol), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 70.6 mg (61.1 μmol), silver carbonate (Ag ₂ CO ₃ ) 284 mg (1.03 mmol) and 30 mL of dry THF were added. The mixture was allowed to react with stirring at 65 ° C. for 24 hours and the mixture was quenched with water. The product was extracted with ethyl acetate (EtOAc) and the organic phase was dried over Na ₂ SO ₄ and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (hexane / EtOAc = 10 / 1-5 / 1) to obtain 290 mg of the target compound as a colorless solid (yield 54%).

¹ H NMR (600 MHz, CDCl ₃ ) δ1.35 (s, 24H), 2.17 (br, 4H), 2.38 (br, 4H), 3.44 (s, 6H), 4.48 (s, 4H), 7.52 (d , J = 8 Hz, 4H), 7.58 (d, J = 8 Hz, 4H), 7.58 (d, J = 8 Hz, 4H), 7.86 (d, J = 8 Hz, 4H); ¹³ C NMR (150 MHz, CDCl ₃ ) δ24.9 (CH ₃ ), 33.1 (CH ₂ ), 56.0 (CH ₃ ), 78.2 (4 °), 83.8 (4 °), 92.3 (CH ₂ ), 126.3 (CH), 127.1 ( CH), 127.3 (br, CH), 135.3 (CH), 140.1 (4 °), 143.2 (4 °); HRMS (FAB) m / z calcd for C ₃₄ H ₅₀ B ₂ NaO ₈ [M ・ Na] ⁺ : 783.4210, found 783.4240.

Synthesis Example 28 Production of Compound (21)

In a 100 ml flask containing a stirrer, 155 mg (204 μmol) of the compound (16a) obtained in Synthesis Example 27, 1.22 g (2.37 mmol) of the compound (5b) obtained in Synthesis Example 2, tetrakis (triphenylphosphine) ) Palladium (0) (Pd (PPh ₃ ) ₄ ) 25.4 mg (22.0 mmol), sodium carbonate (Na ₂ CO ₃ ) 107 mg (1.01 mmol), dry toluene 12 mL, and dry ethyl acetate (EtOAc) 3 mL. I put it in. The mixture was reacted for 24 hours at 70 ° C. with stirring. After cooling to room temperature, the mixture was concentrated under reduced pressure. The product was extracted with ethyl acetate (EtOAc), dried over Na ₂ SO ₄ and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (hexane / EtOAc = 6/1 to 1/1) to obtain 239 mg of the target compound as a colorless solid (44% yield).

¹ H NMR (600 MHz, CDCl ₃ ) δ2.10 (br, 12H), 2.27-2.49 (m, 12H), 3.41 (s, 6H), 3.43 (s, 6H), 3.45 (s, 6H), 4.43 (s, 4H), 4.47 (s, 4H), 4.50 (s, 4H), 7.32 (d, J = 8 Hz, 4H), 7.44 (d, J = 8 Hz, 4H), 7.50 (d, J = 8 Hz, 4H), 7.54 (d, J = 8 Hz, 4H), 7.59 (d, J = 8 Hz, 4H), 7.60 (d, J = 8 Hz, 4H), 7.64 (s, 8H); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 33.0 (CH ₂ ), 56.0 (CH ₃ ), 77.9 (4 °), 78.1 (4 °), 78.2 (4 °), 92.2 (CH ₂ ), 92.3 (CH ₂ ), 121.7 (4 °), 126.9 (CH), 126.9 (CH), 127.4 (CH), 127.4 (CH), 128.7 (CH), 131.5 (CH), 139.4 (4 °), 139.5 (4 °), 139.7 (4 °), 139.8 (4 °), 141.6 (br, 4 °); HRMS (FAB) m / z calcd for C ₇₆ H ₈₆ Br ₂ NaO ₈ [M ・ Na] ⁺ : 1395.4378, found 1395.4364.

Synthesis Example 29: Production of compound (15a)

In a 50 ml round bottom glass flask containing a stirrer, 102 mg (98.2 μmol) of the compound (8a) obtained in the above Synthesis Example 9 and 500 mg (972 μmol) of the compound (5b) obtained in the above Synthesis Example 2 were added. ), Tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) 11.1 mg (9.60 μmol), silver carbonate (Ag ₃ CO ₃ ) 108 mg (355 μmol), and dry THF 10 mL. Thereafter, the obtained mixture was reacted at 60 ° C. for 19 hours while stirring. The reaction mixture was cooled to room temperature and then quenched with water. Then extracted with ethyl acetate (EtOAc) and the organic phase was dried over Na ₂ SO ₄ and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (hexane / EtOAc = 3/1 to 2/3) to obtain 93.9 mg of the target compound as a colorless solid (yield 58%).

¹ H NMR (600 MHz, CDCl ₃ ) δ2.15 (br, 16H), 2.27-2.42 (m, 16H), 3.40 (s, 6H), 3.41 (s, 6H), 3.43 (s, 6H), 3.44 (s, 6H), 4.43 (s, 4H), 4.45 (s, 4H), 4.47 (s, 4H), 4.49 (s, 4H), 7.31 (d, J = 8 Hz, 4H), 7.43 (d, J = 8 Hz, 4H), 7.45-7.56 (m, 20H), 7.59 (d, J = 8 Hz, 4H), 7.63 (s, 4H); HRMS (FAB) m / z calcd for C ₉₄ H ₁₀₈ Br ₂ NaO ₁₆ [M ・ Na] ⁺ : 1673.5896, found 1673.5862.

Synthesis Example 30 Production of Ring-shaped Compound (12b-1) (Part 2)

In a 50 ml round bottom glass flask containing a stir bar, 14.5 mg (52.7 μmol) of bis (1,5-cyclooctadiene) nickel (0) (Ni (cod) ₂ ), obtained by Synthesis Example 25 above. 30.6 mg (25.0 μmol) of the compound (14-1) and 7.82 mg (50.1 μmol) of 2,2′-bipyridyl were added. Thereafter, 15.5 mL of dry THF was added. The resulting mixture was reacted under reflux for 24 hours with stirring. The reaction mixture was cooled to room temperature, then filtered through silica gel, washed with ethyl acetate (EtOAc), and then the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (hexane / EtOAc) to obtain 12.2 mg of the target compound as a colorless solid (yield 46%).

Synthesis Example 31 Production of Ring-shaped Compound (20a-1) (Part 1)

In a 50 ml round bottom glass flask containing a stir bar, 21.0 mg (40.9 μmol) of the compound (5b) obtained in Synthesis Example 2 and 49.4 mg (47.6 mg) of the compound (8a) obtained in Synthesis Example 9 were obtained. μmol), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂ (dba) ₃ ) 3.8 mg (8.0 μmol), potassium phosphate (K ₃ PO ₄ ) 84.9 mg (405 μmol), 1,4-dioxane 20 mL And 80 μL of water. Thereafter, the resulting mixture was reacted at 80 ° C. for 24 hours while stirring. The reaction mixture was cooled to room temperature, then filtered through a silica gel layer, washed with ethyl acetate (EtOAc), and then the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (chloroform) and preparative thin layer chromatography (CHCl 3 / EtOAc = 1/1) to obtain 9.3 mg of the target compound as a colorless solid (yield 20%).

¹ H NMR (600 MHz, CD ₂ Cl ₂ , 35 ° C) δ 1.67 (s, 4H), 1.93-2.53 (m, 20H), 2.31 (br, 4H), 3.36 (s, 6H), 3.37 (s, 6H), 3.45 (s, 6H), 4.48 (s, 4H), 4.55 (s, 4H), 4.58 (s, 4H), 7.29 (d, J = 8 Hz, 4H), 7.40-7.47 (m, 12H ), 7.60 (d, J = 8 Hz, 4H), 7.66 (d, J = 8 Hz, 4H), 7.68 (s, 4H); ¹³ C NMR (150 MHz, CDCl ₃ , 50 ° C) δ32.8 ( CH ₂ ), 33.2 (CH ₂ ), 34.0 (CH ₂ ), 55.5 (CH ₃ ), 55.9 (CH ₃ ), 56.2 (CH ₃ ), 77.9 (4 °), 78.3 (4 °), 78.4 (4 ° ), 92.2 (CH ₂ ), 92.3 (CH ₂ ), 92.6 (CH ₂ ), 126.6 (CH), 126.8 (CH), 126.8 (CH), 127.2 (CH), 127.3 (CH), 128.3 (CH), 139.3 (4 °), 139.3 (4 °), 139.5 (4 °), 139.5 (4 °); HRMS (FAB) m / z calcd for C ₃₄ H ₅₀ B ₂ NaO ₈ [M ・ Na] ⁺ : 631.3584, found 631.3605.

Synthesis Example 32 Production of Compound (20a-1) (Part 2)

In a 50 ml Schlenk tube containing a stirrer, 29.5 mg (24.1 μmol) of the compound (14-1) obtained in Synthesis Example 25, compound (6d) (bis (pinacol) 1,4-benzenediboronate) Ester, 1,4-benzenediboronic acid bis (pinacol) ester) 11.1 mg (33.6 μmol), palladium acetate (II) (Pd (OAc) ₂ ) 2.15 mg (9.58 μmol), 2- (dicyclohexylphosphino) -2 ′ 4,4 ′, 6′-triisopropyl-1,1′-biphenyl (X-Phos) 4.57 mg (9.59 μmol), 10 M NaOH aqueous solution 20.0 mL (200 μmol) and 1,4-dioxane 20 mL were added. Thereafter, the resulting mixture was reacted at 80 ° C. for 17 hours while stirring. Further water was added and extracted with ethyl acetate (EtOAc), the organic phase was dried over Na ₂ SO ₄ and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (chloroform) and preparative thin layer chromatography (CHCl 3 / EtOAc = 1/1) to obtain 5.04 mg of the target compound as a colorless solid (yield 18%).

¹ H NMR (600 MHz, CD ₂ Cl ₂ , 35 ° C) δ 1.67 (s, 4H), 1.93-2.53 (m, 20H), 2.31 (br, 4H), 3.36 (s, 6H), 3.37 (s, 6H), 3.45 (s, 6H), 4.48 (s, 4H), 4.55 (s, 4H), 4.58 (s, 4H), 7.29 (d, J = 8 Hz, 4H), 7.40-7.47 (m, 12H ), 7.60 (d, J = 8 Hz, 4H), 7.66 (d, J = 8 Hz, 4H), 7.68 (s, 4H); ¹³ C NMR (150 MHz, CDCl ₃ , 50 ° C) δ32.8 ( CH ₂ ), 33.2 (CH ₂ ), 34.0 (CH ₂ ), 55.5 (CH ₃ ), 55.9 (CH ₃ ), 56.2 (CH ₃ ), 77.9 (4 °), 78.3 (4 °), 78.4 (4 ° ), 92.2 (CH ₂ ), 92.3 (CH ₂ ), 92.6 (CH ₂ ), 126.6 (CH), 126.8 (CH), 126.8 (CH), 127.2 (CH), 127.3 (CH), 128.3 (CH), 139.3 (4 °), 139.3 (4 °), 139.5 (4 °), 139.5 (4 °); HRMS (FAB) m / z calcd for C ₃₄ H ₅₀ B ₂ NaO ₈ [M ・ Na] ⁺ : 631.3584, found 631.3605.

Synthesis Example 33: Production of compound (19a)

In a 20 ml J-Young Schlenk tube containing a stir bar, 70.0 mg (50.9 μmol) of the compound (21) obtained in Synthesis Example 28 above, bis (1,5-cyclooctadiene) nickel (0) (Ni (cod) ₂ ) 48.2 mg (17.5 μmol), 2,2′-bipyridyl (2,2′-bipyridyl) 27.1 mg (17.3 μmol), and 2 mL of dry 1,4-dioxane were added. Thereafter, the resulting mixture was reacted at 80 ° C. for 24 hours while stirring. After cooling to room temperature, the mixture was concentrated under reduced pressure. The product was extracted with ethyl acetate (EtOAc), dried over Na ₂ SO ₄ and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (CHCl ₃ / EtOAc = 2/1) to obtain 26.1 mg of the target compound as a colorless solid (yield 42%).

¹ H NMR (600 MHz, CDCl ₃ , 50 ° C) δ 1.86 (br, 4H), 2.08 (br, 4H), 2.21-2.47 (m, 16H), 3.39 (s, 6H), 3.44 (s, 6H) , 3.44 (s, 6H), 4.52 (s, 4H), 4.54 (s, 4H), 4.62 (s, 4H), 7.35 (d, J = 8 Hz, 4H), 7.42 (d, J = 8 Hz, 4H), 7.44 (d, J = 8 Hz, 4H), 7.54 (d, J = 8 Hz, 8H), 7.56-7.62 (m, 16H); ¹³ C NMR (150 MHz, CDCl ₃ , 50 ° C) δ 32.8 (CH ₂ ), 33.4 (CH ₂ ), 33.7 (CH ₂ ), 55.7 (CH ₃ ), 55.8 (CH ₃ ), 56.2 (CH ₃ ), 77.9 (4 ^o ), 78.0 (4 ^o ), 78.3 ( 4 ^o ), 92.2 (CH ₂ ), 92.4 (CH ₂ ), 92.5 (CH ₂ ), 126.8 (CH), 126.8 (CH), 126.8 (CH), 126.9 (CH), 127.2 (CH), 127.3 (CH ), 127.5 (CH), 127.9 (CH), 139.2 (4 °), 139.3 (4 °), 139.4 (4 °), 139.5 (4 °), 139.6 (4 °); HRMS (FAB) m / z calcd for C ₇₆ H ₈₆ NaO ₈ [M ・ Na] ⁺ : 1237.6011, found 1237.6014.

Synthesis Example 34 Production of Compound (18a)

In a 50 ml round bottom glass flask containing a stir bar, 41.3 mg (25.0 μmol) of the compound (15a) obtained in Synthesis Example 29 above, bis (1,5-cyclooctadiene) nickel (0) (Ni ( cod) ₂ ) 13.8 mg (50.2 μmol) and 2,2′-bipyridyl (2,2′-bipyridyl) were added. After adding 12.5 mL of dry THF, the resulting mixture was reacted under reflux for 24 hours with stirring. The reaction mixture was cooled to room temperature, then filtered through silica gel, washed with ethyl acetate (EtOAc), and then the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography (hexane / EtOAc) to obtain 19.0 mg of the target compound as a colorless solid (yield 51%).

¹ H NMR (600 MHz, CDCl ₃ , 50 ° C) δ 1.90-2.46 (m, 32H), 3.38 (s, 6H), 3.40 (s, 6H), 3.40 (s, 6H), 3.45 (s, 6H) , 4.40 (s, 4H), 4.42 (s, 4H), 4.50 (s, 4H), 4.52 (s, 4H), 7.42 (d, J = 8 Hz, 4H), 7.45-7.52 (m, 20H), 7.55 (d, J = 8 Hz, 4H), 7.59 (d, J = 8 Hz, 4H), 7.63 (s, 4H); HRMS (FAB) m / z calcd for C ₉₄ H ₁₀₈ NaO ₈ [M ・ Na ] ⁺ : 1515.7535, found 1515.7530.

Synthesis Example 35: Production of [10] cycloparaphenylene (13a)

In a Schlenk tube with a 20 mL stirrer and a condenser, 9.3 mg (8.2 μmol) of the compound (20a-1) obtained in Synthesis Example 31 or 32 above, sodium hydrogen sulfate monohydrate (NaHSO ₄ .H ₂₎ O) 28 mg (20 μmol), dry dimethyl sulfoxide (DMSO) 1.5 mL and dry m-xylene 5 mL were added and heated at 150 ° C. for 72 hours with stirring. After cooling to room temperature, it was quenched with saturated aqueous sodium bicarbonate (NaHCO ₃ ), filtered through celite using ethyl acetate (EtOAc) as a solvent, and extracted with ethyl acetate (EtOAc). Furthermore, the organic phase was dried over Na ₂ SO ₄ and then concentrated under reduced pressure. Thereafter, 1.5 mg of the target compound as a yellow solid was obtained by TLC (hexane / CH ₂ Cl ₂ = 1/1) (yield 24%).

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.56 (s, 40H); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 127.4 (CH), 138.2 (4 °); HRMS (MALDI) m / z calcd for C ₆₀ H ₄₀ [M ・] ⁺ : 760.3125, found: 760.3153.

Synthesis Example 36: Production of [11] cycloparaphenylene (13b)

In a Schlenk tube with a 20 mL stirrer and condenser, 20.7 mg (17.0 μmol) of the compound (19a) obtained in Synthesis Example 33 above, 51.6 mg of sodium bisulfate monohydrate (NaHSO ₄ .H ₂ O) (37.4 μmol), 20.7 mg (84.2 μmol) of o-chloranil, 1.5 mL of dry dimethyl sulfoxide (DMSO) and 4 mL of dry m-xylene were added. The mixture was heated at 150 ° C. for 48 hours with stirring. After cooling to room temperature, it was quenched with saturated aqueous sodium bicarbonate (NaHCO ₃ ) and filtered through celite using ethyl acetate (EtOAc) as a solvent. The product was extracted with ethyl acetate (EtOAc). Furthermore, the organic phase was dried over Na ₂ SO ₄ and then concentrated under reduced pressure. Then, 4.6 mg of the target compound as a yellow solid was obtained by TLC (hexane / CH ₂ Cl ₂ = 1/1) (yield 32%).

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.58 (s, 44H); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 127.3 (CH), 138.4 (4 °); HRMS (MALDI) m / z calcd for C ₆₆ H ₄₄ [M ・] ⁺ : 836.3438, found: 836.3437.

Synthesis Example 37: Production of [13] cycloparaphenylene (13c)

A stirrer and a condenser with Schlenk tube 20 mL, compounds obtained by the above Synthesis Example 34 (18a) 4.0 mg (2.7μmol ), sodium bisulfate monohydrate _{(NaHSO 4 · H 2 O)} 7.4 mg (54 μmol), o-chloranil (3.3 mg, 13 μmol), dry dimethyl sulfoxide (DMSO) (1.5 mL) and dry m-xylene (4 mL) were added. The mixture was heated at 150 ° C. for 48 hours with stirring. After cooling to room temperature, it was quenched with saturated aqueous sodium bicarbonate (NaHCO ₃ ) and filtered through celite using ethyl acetate (EtOAc) as a solvent. The product was extracted with ethyl acetate (EtOAc) and the organic phase was dried over Na ₂ SO ₄ and then concentrated under reduced pressure. Then, 9.3 mg of the target compound as a yellow solid was obtained by TLC (hexane / CH ₂ Cl ₂ = 1/1) (yield 20%).

¹ H NMR (600 MHz, CDCl ₃ ) δ 7.64 (s, 52H); ¹³ C NMR (150 MHz, CDCl ₃ ) δ 127.4 (CH), 138.7 (4 °); HRMS (MALDI) m / z calcd for C ₇₈ H ₅₂ [M ・] ⁺ : 988.4064, found: 988.4086.

Example 1 ([12] cycloparaphenylene → CNT)
A toluene solution (0.001 wt%) of [12] cycloparaphenylene ([12] CPP) (4a) obtained in Synthesis Example 23 (3) was applied on a sapphire single crystal substrate (C surface) by spin coating. did. The spin coating conditions were a rotation speed of 4000 rpm and a rotation time of 60 seconds.

  The prepared [12] CPP-coated sapphire single crystal substrate was placed at the end of a quartz reaction tube, and then the inside of the reaction tube was evacuated (final ultimate pressure was about 0.01 torr (about 1.33 Pa)) . Subsequently, ethanol was supplied to the reaction tube (pressure 7 torr (933.25 Pa)), and the central part was heated to 500 ° C. in an electric furnace. After waiting for the temperature and ethanol supply to stabilize, the sapphire substrate coated with [12] CPP was quickly moved to the center of the reaction tube to start nanotube growth by chemical vapor deposition (CVD). 15 minutes after the start of the reaction, the growth of the nanotube was terminated by moving the sapphire single crystal substrate from the central part of the reaction tube at 500 ° C. to the end part at room temperature.

  The formation and structure of the carbon nanotubes were evaluated by transmission electron microscope (TEM) observation and Raman spectroscopy. The transmission electron microscope used was JEOL JEM-2100F / HR, and the Raman spectrometer used Horiba Jobin Yvon LabRAM HR-800.

  The observation results of the transmission electron microscope are shown in FIGS. When the diameters of the CNTs obtained from these figures were measured, it was confirmed that CNTs having a substantially uniform diameter were obtained (FIG. 4). From FIG. 4, it was confirmed that CNTs having a diameter of 1.5 to 1.6 nm were selectively generated from [12] cycloparaphenylene as a raw material.

  The physical properties of CNT were measured by Raman spectroscopy. In Raman spectroscopy, the detected CNT differs depending on the excitation wavelength of the laser used for excitation. FIG. 5 shows the results of evaluating CNTs using lasers having excitation wavelengths of 488 nm, 514 nm, and 633 nm. The diameter of the synthesized CNT was about 1.6 nm. When the excitation wavelengths were 488 nm and 514 nm, semiconducting CNT was detected, and when the excitation wavelength was 633 nm, metallic CNT was detected. From FIG. 5, Raman bands peculiar to CNT were observed when 488 and 633 nm were used as excitation wavelengths. That is, it was confirmed that the CNT obtained this time has a property in which both semiconductor properties and metallic properties are mixed.

Example 2 ([9] cycloparaphenylene → CNT)
A toluene solution (0.001 wt%) of [9] cycloparaphenylene ([9] CPP) (4b) obtained in Synthesis Example 23 (2) was applied on a sapphire single crystal substrate (C surface) by spin coating. did. The spin coating conditions were a rotation speed of 4000 rpm and a rotation time of 60 seconds.

  The prepared [9] CPP-coated sapphire single crystal substrate was placed at the end of a quartz reaction tube, and then the inside of the reaction tube was evacuated (final ultimate pressure was about 0.01 torr (about 1.33 Pa)) . Subsequently, ethanol was supplied to the reaction tube (pressure 7 torr (933.25 Pa)), and the central part was heated to 500 ° C. in an electric furnace. After waiting for the temperature and ethanol supply to stabilize, the sapphire substrate coated with [9] CPP was quickly moved to the center of the reaction tube to start nanotube growth by chemical vapor deposition (CVD). 15 minutes after the start of the reaction, the growth of the nanotube was terminated by moving the sapphire single crystal substrate from the central part of the reaction tube at 500 ° C. to the end part at room temperature.

  The formation of carbon nanotubes and their structure were evaluated by Raman spectroscopy. The Raman spectrometer used was LabRAM HR-800 manufactured by Horiba Jobin Yvon.

  The physical properties of CNT were measured by Raman spectroscopy. FIG. 6 shows the results of evaluating CNTs using lasers having excitation wavelengths of 488 nm, 514 nm, and 633 nm. When the excitation wavelength was 488 nm and 514 nm, semiconducting CNT was detected, and when the excitation wavelength was 633 nm, metallic CNT was detected. From FIG. 6, Raman bands peculiar to CNT were observed when 488, 514, and 633 nm were used as excitation wavelengths.

Example 3 ([14] cycloparaphenylene → CNT)
CNT obtained by treating [14] cycloparaphenylene (3a) obtained in Synthesis Example 12 or 13 in the same manner as in Example 1.

Example 4 ([15] cycloparaphenylene → CNT)
CNT obtained by treating [15] cycloparaphenylene (3b) obtained in Synthesis Example 15 or 16 in the same manner as in Example 1.

Example 5 ([16] cycloparaphenylene → CNT)
CNT obtained by treating [16] cycloparaphenylene (3c) obtained in Synthesis Example 18 in the same manner as in Example 1.

Example 6 ([14] cycloparaphenylene → CNT containing one naphthylene)
CNT which processed the compound (3d) obtained by the synthesis example 22 like Example 1. FIG.

Example 7 ([10] cycloparaphenylene → CNT)
CNT obtained by treating [10] cycloparaphenylene (13a) obtained in Synthesis Example 35 in the same manner as in Example 1.

Example 8 ([11] cycloparaphenylene → CNT)
CNT obtained by treating [11] cycloparaphenylene (13b) obtained in Synthesis Example 36 in the same manner as in Example 1.

Example 9 ([13] cycloparaphenylene → CNT)
CNT obtained by treating [13] cycloparaphenylene (13c) obtained in Synthesis Example 37 in the same manner as in Example 1.

Claims (8)

A method for producing a carbon nanotube, comprising reacting a carbon source with a cyclic compound formed by connecting a plurality of aromatic rings, wherein the reaction supplies a gaseous carbon source without using a catalyst. However, the manufacturing method of making it heat-process at 400-1200 degreeC under the pressure of 10 < ^-4 > -10 < ⁵ > Pa, and performing chemical vapor deposition . The production method according to claim 1, wherein the cyclic compound formed by connecting the plurality of aromatic rings is a cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups. The cyclic compound (carbon nanoring) formed by connecting a plurality of divalent aromatic hydrocarbon groups is a cycloparaphenylene compound, or at least one phenylene group of the cycloparaphenylene compound is a divalent condensed polycycle. The production method according to claim 2, which is a modified cycloparaphenylene compound substituted with an aromatic hydrocarbon group. The cyclic compound (carbon nanoring) formed by connecting the plurality of divalent aromatic hydrocarbon groups is represented by the general formula (1):

(In the formula, a represents an integer of 6 or more.)
Or at least one phenylene group of the cycloparaphenylene compound represented by the general formula (1) is represented by the general formula (2):

(In the formula, b represents an integer of 1 or more.)
The manufacturing method of Claim 3 which is the modified cycloparaphenylene compound substituted by group represented by these. The manufacturing method of Claim 4 whose said cycloparaphenylene compound is a compound whose a in General formula (1) is an integer of 6-100. The production according to claim 4 or 5, wherein the cyclic compound (carbon nanoring) formed by linking the plurality of divalent aromatic hydrocarbon groups is a cycloparaphenylene compound represented by the general formula (1). Method. The cyclic compound (carbon nanoring) formed by connecting the plurality of divalent aromatic hydrocarbon groups is represented by the general formula (3)

Wherein R ² is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; R ⁴ is the same or different and each is a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon Group is the same or different, and each is an integer of 0 or more; n is the same or different and each represents an integer of 1 or more.)
A cyclic compound represented by the general formula (4):

(In the formula, d represents an integer of 1 or more.)
Or a cyclic compound represented by the general formula (13):

[Wherein R ⁷ is the same or different and each represents a phenylene group or a divalent condensed polycyclic aromatic hydrocarbon group; l is 10, 11 or 13; ]
The manufacturing method of Claim 2 which is a cyclic compound shown by these. The production method according to claim 1, wherein the carbon source is at least one selected from the group consisting of a hydrocarbon compound, an alcohol compound, an ether compound, and an ester compound.

Images